Nanometer-sized clusters are often targeted due to their potential applications as nanoreactors or storage/delivery devices. One route to assemble and stabilize finite structures consists in imparting directional bonding patterns between the nanoparticles. When only a portion of the particle surface is able to form an inter-particle bond, finite-size aggregates such as micelles and vesicles may form. Building on this approach, we combine particle shape anisotropy with the directionality of the bonding patterns and investigate the combined effect of particle elongation and surface patchiness on the low density assembly scenario. To this aim, we study the assembly of tip-functionalised Janus hard spherocylinder by means of Monte Carlo simulations. By exploring the effects of changing the interaction strength and range at different packing fractions, we highlight the role played by shape and bond anisotropy on the emerging aggregates (micelles, vesicles, elongated micelles and lamellae). We observe that shape anisotropy plays a crucial role in suppressing phases that are typical to spherical Janus nanoparticles and that a careful tuning of the interaction parameters allows to promote the formation of spherical micelles. These finite-size spherical clusters composed of elongated particles might offer more interstitials and larger surface areas than those offered by micelles of spherical or almost-spherical units, thus enhancing their storage and catalytic properties.
We present a novel computational framework for simulating suspensions of rigid spherical Janus particles in Stokes flow. We show that long-range Janus particle interactions for a wide array of applications may be resolved using fast, spectrally accurate boundary integral methods tailored to polydisperse suspensions of spherical particles. These are incorporated into our rigid body Stokes platform. Our approach features the use of spherical harmonic expansions for spectrally accurate integral operator evaluation, complementarity-based collision resolution, and optimal O(n) scaling with the numb…
Aging in a two dimensional suspension containing rods was studied by means of kinetic Monte Carlo simulations. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The initial state was produced using a random sequential adsorption model. During the aging, the rods underwent translational and rotational Brownian motions. The simulations were run at different values of number density (the number of rods per unit area), $ρ$, and of the initial orientation order parameter, $S_i$. The rods were assumed to have core---shell structures. The evolutions …
The sedimentation of a two dimensional suspension containing rods was studied by means of kinetic Monte Carlo (MC) simulations. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The initial state before sedimentation was produced using a model of random sequential adsorption. During such sedimentation, the rods undergo translational and rotational Brownian motions. The MC simulations were run at different initial number densities (the numbers of rods per unit area), $ρ_i$, and sedimentation rates, $u$. For sediment films, the spatial distribut…
There is now convincing evidence that inter-particle frictional contacts are essential for observing shear-thickening in concentrated suspensions of compact particles. While this has inspired many strategies to tailor the rheology in these systems, in the more general case, viz-a-viz suspensions of anisotropic particles, the mechanism of shear-thickening remains unclear. Here through simultaneous measurements of the bulk viscosity and the first Normal stress difference, we show that strong shear thickening in suspensions of colloidal rods is accompanied by large positive normal stresses, indic…
We compute the entropic interactions between two colloidal spheres immersed in a dilute suspension of semi-flexible rods. Our model treats the semi-flexible rod as a bent rod at fixed angle, set by the rod contour and persistence lengths. The entropic forces arising from this additional rotational degree of freedom are captured quantitatively by the model, and account for observations at short range in a recent experiment. Global fits to the interaction potential data suggest the persistence length of fd-virus is about two to three times smaller than the commonly used value of $2.2 μ{m}$.
We investigate confined shear thickening suspensions for which the sample thickness is comparable to the particle dimensions. Rheometry measurements are presented for densely packed suspensions of spheres and rods with aspect ratios 6 and 9. By varying the suspension thickness in the direction of the shear gradient at constant shear rate, we find pronounced oscillations in the stress. These oscillations become stronger as the gap size is decreased, and the stress is minimized when the sample thickness becomes commensurate with an integer number of particle layers. Despite this confinement-indu…
In a mixed suspension of rods and small polymer coils, the rods adsorb onto a hard wall in contact with the suspension. This adsorption is studied in the low density of rods limit. It is driven by depletion forces and is much stronger for long rods than for spheres. This is shown by means of exact, numerical, calculations and an approximate theory.
Isotropic-Nematic and Nematic-Nematic transitions from a homogeneous base state of a suspension of high aspect ratio, rod-like magnetic particles are studied for both Maier-Saupe and the Onsager excluded volume potentials. A combination of classical linear stability and asymptotic analyses provides insight into possible nematic states emanating from both the isotropic and nematic non-polarized equilibrium states. Local analytical results close to critical points in conjunction with global numerical results (Bhandar, 2002) yields a unified picture of the bifurcation diagram and provides a conve…
The short--time self diffusion coefficient of a sphere in a suspension of rigid rods is calculated in first order in the rod volume fraction. For low rod concentrations the correction to the Einstein diffusion constant of the sphere is a linear function of the rod volume fraction with the slope proportional to the equilibrium averaged mobility diminution trace of the sphere interacting with a single freely translating and rotating rod. The two--body hydrodynamic interactions are calculated using the so--called bead model in which the rod is replaced by a stiff linear chain of touching spheres.…
We present a study of the isotropic-nematic interface in a system of hard spherocylinders. First we compare results from Monte Carlo simulations and Onsager density functional theory for the interfacial profiles of the orientational order parameter and the density. Those interfacial properties that are not affected by capillary waves are in good agreement, despite the fact that Onsager theory overestimates the coexistence densities. Then we show results of a Monte Carlo study of the capillary waves of the interface. In agreement with recent theoretical investigations (Eur.Phys.J. E {\bf 18} 40…
By developing a molecular dynamics model of bacterial chemotaxis, we present the first investigation of tracer statistics in bacterial suspensions where chemotactic effects are considered. We demonstrate that the non-Gaussian statistics of full-coated tracer arises from the athermal bacterial noise. Moreover, Janus (half-coated) tracer performs a composite random walk combining power-law-tail distributed Lévy flights with Brownian jiggling at low coating concentration, but turns to an enhanced directional transport (EDT) when coating concentration is high. Unlike conventional self-propelled pa…
Above a certain density threshold, suspensions of rod-like colloidal particles form system-spanning networks. Using Monte Carlo simulations, we investigate how the depletion forces caused by spherical particles affect these networks in isotropic suspensions of rods. Although the depletion forces are strongly anisotropic and favor alignment of the rods, the percolation threshold of the rods decreases significantly. The relative size of the effect increases with the aspect ratio of the rods. The structural changes induced in the suspension by the depletant are characterized in detail and the sys…
In order to investigate the coupling between the degrees of alignment of elongated particles in binary nematic dispersions, surfactant stabilized single-wall carbon nanotubes (CNTs) have been added to nematic suspensions of colloidal rodlike viruses in aqueous solution.We have independently measured the orientational order parameter of both components of the guest-host system by means of polarized Raman spectroscopy and by optical birefringence, respectively. Our system allows us therefore to probe the regime where the guest particles (CNTs) are shorter and thinner than the fd virus host parti…
We present a study of connectivity percolation in suspensions of hard spherocylinders by means of Monte Carlo simulation and connectedness percolation theory. We focus attention on polydispersity in the length, the diameter and the connectedness criterion, and invoke bimodal, Gaussian and Weibull distributions for these. The main finding from our simulations is that the percolation threshold shows quasi universal behaviour, i.e., to a good approximation it depends only on certain cumulants of the full size and connectivity distribution. Our connectedness percolation theory hinges on a Lee-Pars…
An active colloid is a suspension of particles that transduce free energy from their environment and use the energy to engage in intrinsically non-equilibrium activities such as growth, replication and self-propelled motility. An obvious example of active colloids is a suspension of bacteria such as Escherichia coli, their physical dimensions being almost invariably in the colloidal range. Synthetic self-propelled particles have also become available recently, such as two-faced, or Janus, particles propelled by differential chemical reactions on their surfaces driving a self-phoretic motion. I…
We study theoretically the effect of a gravitational field on the equilibrium behaviour of a colloidal suspension of rods with different length-to-width aspect ratios. The bulk phases of the system are described with analytical equations of state. The gravitational field is then incorporated via sedimentation path theory, which assumes a local equilibrium condition at each altitude of the sample. The bulk phenomenology is significantly enriched by the presence of the gravitational field. In a suspension of elongated rods with five stable phases in bulk, the gravitational field stabilizes up to…
We study by simulation and theory how the addition of insulating spherical particles affects the conductivity of fluids of conducting rods, modeled by spherocylinders. The electrical connections are implemented as tunneling processes, leading to a more detailed and realistic description than a discontinuous percolation approach. We find that the spheres enhance the tunneling conductivity for a given concentration of rods and that the enhancement increases with rod concentration into the regime where the conducting network is well established. By reformulating the network of rods using a critic…
Suspensions of non-Brownian rods: droplet pinch-off, onset of heterogeneity and effective extensional viscosity
PMMH, CNRS, ESPCI Paris, Sorbonne Université, Université Paris-Cité（PMHH，法国国家科学研究中心，巴黎高等物理化工学院，索邦大学，巴黎 Cité 大学）；Department of Mechanical Engineering, University of California, Santa Barbara（加州大学圣塔芭芭拉分校机械工程系）；Institute of Physics, University of Amsterdam（阿姆斯特丹大学物理研究所）；Department of Mechanical Engineering, University of Maryland（马里兰大学机械工程系）；Department of Chemical and Biomolecular Engineering, University of Maryland（马里兰大学化学与生物分子工程系）
The rheology of nanoparticle suspensions for nanoparticles of various shapes with equal mass is studied using molecular dynamics simulations. The equilibrium structure and the response to imposed shear are analyzed for suspensions of spheres, rods, plates, and jacks in an explicit solvent for both charged and uncharged nanoparticles. For the volume fraction studied, ?$ϕ_{vf}=0.075$, the uncharged systems are all in their isotropic phase and the viscosity is only weakly dependent on shape for spheres, rods, and plate whereas for the jacks the viscosity is an order of magnitude larger than for t…
We investigate geometric percolation and scaling relations in suspensions of nanorods, covering the entire range of aspect ratios from spheres to extremely slender needles. A new version of connectedness percolation theory is introduced and tested against specialized Monte Carlo simulations. The theory accurately predicts percolation thresholds for aspect ratios as low as 10. The percolation threshold for rod-like particles of aspect ratios below 1000 deviates significantly from the inverse aspect ratio scaling prediction, thought to be valid in the limit of infinitely slender rods and often u…
We study suspensions of semi-flexible colloidal rods and biopolymers using an Onsager-type second-virial functional for a segmented-chain model. For suspensions of thin and thick fd virus particles we calculate phase diagrams in quantitative agreement with experimental observations, and we find their effective state-point dependent shape to be much shorter and thicker than the actual shape. We also calculate the stretching of worm-like micelles in a host fd virus solution, again finding agreement with experiments. For both systems, our results show that the fd virus stiffness can play a key ro…
When non-adsorbing polymers are added to an isotropic suspension of rod-like colloids, the colloids effectively attract each other via depletion forces. We performed Monte Carlo simulations to study the phase diagram of such rod-polymer mixture. The colloidal rods were modelled as hard spherocylinders; the polymers were described as spheres of the same diameter as the rods. The polymers may overlap with no energy cost, while overlap of polymers and rods is forbidden. Large amounts of depletant cause phase separation of the mixture. We estimated the phase boundaries of isotropic-isotropic coexi…
We present experimental measurements of the cholesteric-smectic phase transition of suspensions of charged semiflexible rods as a function of rod flexibility and surface charge. The rod particles consist of the bacteriophage M13 and closely related mutants, which are structurally identical to this virus, but vary either in contour length and therefore ratio of persistence length to contour length, or vary in surface charge. Surface charge is altered in two ways; by changing solution pH and by comparing M13 with {\it fd} virus, a mutant which differs from M13 only by the substitution of a singl…
We study the temperature field and the resulting flow pattern in the vicinity of a heated metal-capped Janus particle. If its thickness exceeds about 10 nm, the cap forms an isotherm and the flow pattern comprises a quadrupolar term that decays with the square of the inverse distance 1/r^2. For much thinner caps the velocity varies as 1/r^3. These findings could be relevant for collective effects in dense suspensions and for the circular tracer motion observed recently in the vicinity of a tethered Janus particle.
Understanding the relaxation dynamics of colloidal suspensions is crucial to identify the elements that influence the mobility of their constituents, assess their macroscopic response across the relevant time and length scales, and thus disclose the fundamentals underpinning their exploitation in formulation engineering. In this work, we specifically assess the impact of long-ranged ordering on the relaxation dynamics of suspensions of soft-repulsive rod-like particles, which are able to self-organise into nematic and smectic liquid-crystalline phases. By performing Dynamic Monte Carlo simulat…
We explore the behavior of micron-scale autophoretic Janus (Au/Pt) rods, having various Au/Pt length ratios, swimming near a wall in an imposed background flow. We find that their ability to robustly orient and move upstream, i.e. to rheotax, depends strongly on the Au/Pt ratio, which is easily tunable in synthesis. Numerical simulations of swimming rods actuated by a surface slip show a similar rheotactic tunability when varying the location of the surface slip versus surface drag. Slip location determines whether swimmers are Pushers (rear-actuated), Pullers (front-actuated), or in between. …
The vertical drying of a colloidal film containing rod-like particles was studied by means of kinetic Monte Carlo (MC) simulation. The problem was approached using a two-dimensional square lattice and the rods were represented as linear $k$-mers (i.e., particles occupying $k$ adjacent sites). The initial state before drying was produced using a model of random sequential adsorption (RSA) with isotropic orientations of the $k$-mers (orientation of the $k$-mers along horizontal $x$ and vertical $y$ directions are equiprobable). In the RSA model, overlapping of the $k$-mers is forbidden. During t…
In this article, we study the phenomenology of a two dimensional dilute suspension of active amphiphilic Janus particles. We analyze how the morphology of the aggregates emerging from their self-assembly depends on the strength and the direction of the active forces. We systematically explore and contrast the phenomenologies resulting from particles with a range of attractive patch coverages. Finally, we illustrate how the geometry of the colloids and the directionality of their interactions can be used to control the physical properties of the assembled active aggregates and suggest possible …
We present an experimental study of the isotropic-nematic phase transition in an aqueous mixture of charged semi-flexible rods (fd virus) and neutral polymer (Dextran). A complete phase diagram is measured as a function of ionic strength and polymer molecular weight. At high ionic strength we find that adding polymer widens the isotropic-nematic coexistence region with polymers preferentially partitioning into the isotropic phase, while at low ionic strength the added polymer has no effect on the phase transition. The nematic order parameter is determined from birefringence measurements and is…
Recently there is strong experimental and theoretical interest in studying the self-assembly and the phase behavior of patchy and of Janus particles, which form colloidal suspensions. Although in this quest a variety of effective interactions have been proposed and used in order to achieve directed assembly, the critical Casimir effect stands out as being particularly suitable in this respect because it provides both attractive and repulsive interactions as well as the potential of a sensitive temperature control of their strength. Specifically, we have calculated the critical Casimir force be…
Janus particles are special types of nano or micro particles possessing at least two surfaces with distinct physical or chemical properties. The most studied Janus particles are the metal-dielectric particles, in which half surface of dielectric particles is coated with a very thin layer of metals. The external electric field induces dipole moment, and consequently the particles exhibit self-assembled dynamic structures in concentrated aqueous suspensions. Here, we study metal-dielectric Janus particles in a nematic liquid crystal under AC electric field and demonstrate a novel method for meas…
We combine percolation theory and Monte Carlo simulation to study in two dimensions the connectivity of an equilibrium lattice model of interacting Janus disks which self-assemble into an orientationally ordered stripe phase at low temperature. As the patch size is increased or the temperature is lowered, clusters of patch-connected disks grow, and a percolating cluster emerges at a threshold. In the stripe phase, the critical clusters extend longer in the direction parallel to the stripes than in the perpendicular direction, and percolation is thus anisotropic. It is found that the critical b…
It is well known that suspensions of particles in a viscous fluid can affect the rheology significantly, producing a pronounced non-Newtonian response even in dilute suspension. However, it is unclear a priori which particle shapes lead to this behaviour. We present two simple symmetry conditions on the shape which are sufficient for a dilute suspension to be Newtonian for all strain sizes and one sufficient for Newtonian behavior for small strains. We also construct a class of shapes out of thin, rigid rods not found by the symmetry argument which share this property for small strains.
We study experimentally and numerically a (quasi) two dimensional colloidal suspension of self-propelled spherical particles. The particles are carbon-coated Janus particles, which are propelled due to diffusiophoresis in a near-critical water-lutidine mixture. At low densities, we find that the driving stabilizes small clusters. At higher densities, the suspension undergoes a phase separation into large clusters and a dilute gas phase. The same qualitative behavior is observed in simulations of a minimal model for repulsive self-propelled particles lacking any alignment interactions. The obse…
We investigate coarse-grained models of suspended self-thermophoretic microswimmers. Upon heating, the Janus spheres, with hemispheres made of different materials, induce a heterogeneous local solvent temperature that causes the self-phoretic particle propulsion. Starting from atomistic molecular dynamics simulations, we verify the coarse-grained description of the fluid in terms of a local molecular temperature field, and its role for the particle's thermophoretic self-propulsion and hot Brownian motion. The latter is governed by effective nonequilibrium temperatures, which are measured from …
Rheology of dense suspensions of granular spherocylinders by particle-based simulation
School of Engineering, University of Edinburgh（爱丁堡大学工程学院）；Syngenta Jealott’s Hill International Research Centre（先正达乔洛特山国际研究中心）；School of Physics and Astronomy, The University of Edinburgh（爱丁堡大学物理与天文学院）
We study the elastic response of concentrated suspensions of rigid wire frame particles to a step strain. These particles are constructed from infinitely thin, rigid rods of length $L$. We specifically compare straight rod-like particles to bent and branched wire frames. In dense suspensions the wire frames are frozen in a disordered state by the topological entanglements between their arms. We present a simple, geometric method to find the scaling of the elastic stress with concentration in these glassy systems. We apply this method to a simple 2D model system where a test particle is placed …
Self-diffusion in isotropic and liquid crystalline phases of fd virus colloidal rods: a combined single particle tracking and differential dynamic microscopy study
We investigated the effects of particle shape on shear thickening in densely packed suspensions. Rods of different aspect ratios and non-convex hooked rods were fabricated. Viscosity curves and normal stresses were measured using a rheometer for a wide range of packing fractions for each shape. Suspensions of each shape exhibit qualitatively similar Discontinuous Shear Thickening. The logarithmic slope of the stress/shear-rate relation increases dramatically with packing fraction and diverges at a critical packing fraction phi_c which depends on particle shape. The packing fraction dependence …
Purely entropic systems such as suspensions of hard rods, platelets and spheres show rich phase behavior. Rods and platelets have successfully been used as models to predict the equilibrium properties of liquid crystals for several decades. Over the past years hard particle models have also been studied in the context of non-equilibrium statistical mechanics, in particular regarding the glass transition, jamming, sedimentation and crystallization. Recently suspensions of hard anisotropic particles also moved into the focus of materials scientists who work on conducting soft matter composites. …
We analyse the time dependent non-linear rheology of a dilute bacterial suspension (e.g. E. coli) for a pair of impulsively started linear flows - simple shear and uniaxial extension. The rheology is governed by the bacterium orientation distribution which satisfies a kinetic equation that includes rotation by the imposed flow, and relaxation to isotropy via rotary diffusion and tumbling. The relevant dimensionless parameters are the Peclet number $Pe\equiv \dotγτ$, which dictates the importance of flow-induced orientation anisotropy, and $τD_r$, which quantifies the relative importance of the…
We introduce a representative minimal model for phoretically interacting active colloids. Combining kinetic theory, linear stability analyses, and a general relation between self-propulsion and phoretic interactions in auto-diffusiophoretic and auto-thermophoretic Janus colloids collapses the parameter space to two dimensions: area fraction and Péclet number. This collapse arises when the lifetime of the self-generated phoretic fields is not too short, and leads to a universal phase diagram showing that phoretic interactions {\it generically} induce pattern formation in typical Janus colloids,…
We construct colloidal ``sticky'' rods from the semi-flexible filamentous fd virus and temperature-sensitive polymers poly(N-isopropylacrylamide) (PNIPAM). The phase diagram of fd-PNIPAM system becomes independent of ionic strength at high salt concentration and low temperature, i.e. the rods are sterically stabilized by the polymer. However, the network of sticky rods undergoes a sol-gel transition as the temperature is raised. The viscoelastic moduli of fd and fd-PNIPAM suspensions are compared as a function of temperature, and the effect of ionic strength on the gelling behavior of fd-PNIPA…
Artificial microswimmers, or "microbots" have the potential to revolutionise non-invasive medicine and microfluidics. Microbots that are powered by self-phoretic mechanisms, such as Janus particles, often harness a solute fuel in their environment. Traditionally, self-phoretic particles are point-like, but slender phoretic rods have become an increasingly prevalent design. While there has been substantial interest in creating efficient asymptotic theories for slender phoretic rods, hitherto such theories have been restricted to straight rods with axisymmetric patterning. However, modern manufa…
We analyze one of the simplest active suspensions with complex dynamics: a suspension of immotile "Extensor" particles that exert active extensile dipolar stresses on the fluid in which they are immersed. This is relevant to several experimental systems, such as recently studied tripartite rods that create extensile flows by consuming a chemical fuel. We first describe the system through a Doi-Onsager kinetic theory based on microscopic modeling. This theory captures the active stresses produced by the particles that can drive hydrodynamic instabilities, as well as the steric interactions of r…
Flow-history-dependent orientational relaxation in dilute polydisperse colloidal rod suspensions
Okinawa Institute of Science and Technology Graduate University（冲绳科学技术大学院大学）；King Abdullah University of Science and Technology（阿卜杜拉国王科技大学）；University of the Basque Country UPV/EHU（巴斯克地区大学）；University of Cambridge（剑桥大学）
To elucidate mechanisms of mesoscopic turbulence exhibited by active particles, we experimentally study turbulent states of non-living self-propelled particles. We realize an experimental system with dense suspensions of asymmetrical colloidal particles (Janus particles) self-propelling on a two-dimensional surface under an AC electric field. Velocity fields of the Janus particles in the crowded situation can be regarded as a sort of turbulence because it contains many vortices and their velocities change abruptly. Correlation functions of their velocity field reveal the coexistence of polar a…
We present a novel approach for characterizing the properties and performance of active matter in dilute suspension as well as in crowded environments. We use Super-Heterodyne Laser-Doppler-Velocimetry (SH-LDV) to study large ensembles of catalytically active Janus particles moving under UV-illumination. SH-LDV facilitates a model-free determination of the swimming speed and direction, with excellent ensemble averaging. In addition we obtain in-formation on the distribution of the catalytic activity. Moreover, SH-LDV operates away from walls and permits a facile correction for multiple scatter…
Dense suspensions of self-propelled rod-like particles exhibit a fascinating variety of non-equilibrium phenomena. By means of computer simulations of a minimal model for rigid self-propelled colloidal rods with variable shape we explore the generic diagram of emerging states over a large range of rod densities and aspect ratios. The dynamics is studied using a simple numerical scheme for the overdamped noiseless frictional dynamics of a many-body system in which steric forces are dominant over hydrodynamic ones. The different emergent states are identified by various characteristic correlatio…
