We study jammed configurations of hard spheres as a function of compression speed using an event-driven molecular dynamics algorithm. We find that during the compression, the pressure follows closely the metastable liquid branch until the system gets arrested into a glass state as the relaxation time exceeds the compression speed. Further compression yields a jammed configuration that can be regarded as the infinite pressure configuration of that glass state. Consequently, we find that the density of jammed packings varies from 0.638 to 0.658 for polydisperse hard spheres and from 0.635 to 0.645 for pure hard spheres upon decreasing the compression rate. This demonstrates that the density at which the systems falls out of equilibrium determines the density at which the system jams at infinite pressure. In addition, we give accurate data for the jamming density as a function of compression rate and size polydispersity.
We consider the consequences of keeping the total surface fixed for a polydisperse system of $N$ hard spheres. In contrast with a similar model (J. Zhang {\it et al.}, J. Chem. Phys. {\bf 110}, 5318 (1999)), the Percus-Yevick and Mansoori equations of state work very well and do not show a breakdown. For high pressures Monte Carlo simulation we show three mechanically stable polydisperse crystals with either a unimodal or bimodal particle-size distributions.
We investigate next nearest neighbor correlations of the contact number in simulations of polydisperse, frictionless packings in two dimensions. We find that discs with few contacting neighbors are predominantly in contact with discs that have many neighbors and vice versa at all packing fractions. This counter-intuitive result can be explained by drawing a direct analogy to the Aboav-Weaire law in cellular structures. We find an empirical one parameter relation similar to the Aboav-Weaire law that satisfies an exact sum rule constraint. Surprisingly, there are no correlations in the radii bet…
We model the packing structure of a marginally jammed bulk ensemble of polydisperse spheres using an extended granocentric mode explicitly taking into account rattlers. This leads to a relation- ship between the characteristic parameters of the packing, such as the mean number of neighbors and the fraction of rattlers, and the radial distribution function g(r). We find excellent agreement between the model predictions for g(r) and packing simulations as well as experiments on jammed emulsion droplets. The observed quantitative agreement opens the path towards a full structural characterization…
We have studied the contact network properties of two and three dimensional polydisperse, frictionless sphere packings at the random closed packing density through simulations. We observe universal correlations between particle size and contact number that are independent of the polydispersity of the packing. This allows us to formulate a mean field version of the granocentric model to predict the contact number distribution P(z). We find the predictions to be in good agreement with a wide range of discrete and continuous size distributions. The values of the two parameters that appear in the …
We consider the effect of intermolecular interactions on the optimal size-distribution of $N$ hard spheres that occupy a fixed total volume. When we minimize the free-energy of this system, within the Percus-Yevick approximation, we find that no solution exists beyond a quite low threshold ($η\thickapprox 0.260$). Monte Carlo simulations reveal that beyond this density, the size-distribution becomes bi-modal. Such distributions cannot be reproduced within the Percus-Yevick approximation. We present a theoretical argument that supports the occurrence of a non-monotonic size-distribution and emp…
The close packing density of log-normal and bimodal distributed, surface-adsorbed particles or discs in 2D is studied by numerical simulation. For small spread in particle size, the system orders in a polycrystalline structure of hexagonal domains. The domain size and the packing density both decrease as the spread in particle size is increased up to 10.5+/-0.5%. From this point onwards the system becomes amorphous, and the close packing density increases again with spread in particle size. We argue that the polycrystalline and amorphous regions are separated by a Kosterlitz-Thouless-type phas…
A general Monte Carlo simulation method of calculating the elastic constants of polydisperse hard-sphere colloidal crystal was developed. The elastic constants of a size polydisperse hard sphere fcc crystal is calculated. The pressure and three elastic constants(C11, C12 and C44) increase significantly with the polydispersity. It was also found from extrapolation that there is a mechanical terminal polydispersity above which a fcc crystal will be mechanically unstable.
We derive an exact, analytic expression for the fourth virial coefficient of a system of polydisperse spheres under the constraint that the smallest sphere has a radius smaller than a given function of the radii of the three remaining particles.
Monte-Carlo simulations and small-angle x-ray scattering experiments were used to determine the phase diagram of aqueous dispersions of titratable nano-colloids with a moderate size polydispersity over a broad range of monovalent salt concentrations, 0.5 mM $\leq c_s \leq$ 50 mM and volume fractions, $ϕ$. Under slow and progressive increase in $ϕ$, the dispersions freeze into a face-centered-cubic (fcc) solid followed unexpectedly by the formation of a body centered cubic (bcc) phase before to melt in a glass forming liquid. The simulations are found to predict very well these observations. Th…
We have discovered the existence of polydisperse High Internal-Phase-Ratio Emulsions (HIPE) in which the internal-phase droplets, present at 95% volume fraction, remain spherical and organize themselves in the available space according to Apollonian packing rules. These polydisperse HIPE are formed during emulsification of surfactant-poor compositions of oil-surfactant-water two-phase systems. Their droplet size-distributions evolve spontaneously towards power laws with the Apollonian exponent. Small-Angle X-Ray Scattering performed on aged HIPEs demonstrated that the droplet packing structure…
Based on the notion of a construction process consisting of the stepwise addition of particles to the pure fluid, a discrete model for the apparent viscosity as well as for the maximum packing fraction of polydisperse suspensions of spherical, non-colloidal particles is derived. The model connects the approaches by Bruggeman and Farris and is valid for large size ratios of consecutive particle classes during the construction process, appearing to be the first model consistently describing polydisperse volume fractions and maximum packing fraction within a single approach. In that context, the …
We study the size-topology relations in random packings of dry adhesive polydisperse microspheres with Gaussian and lognormal size distributions through a geometric tessellation. We find that the dependence of the neighbour number on the centric particle size is always quasilinear, independent of the size distribution, the size span or interparticle adhesion. The average local packing fraction as a function of normalized particle size for different size variances is well regressed on the same profile, which grows to larger values as the relative strength of adhesion decreases. As for the local…
Volvox barberi is a multicellular green alga forming spherical colonies of 10000-50000 differentiated somatic and germ cells. Here, I show that these colonies actively self-organize over minutes into "flocks" that can contain more than 100 colonies moving and rotating collectively for hours. The colonies in flocks form two-dimensional, irregular, "active crystals", with lattice angles and colony diameters both following log-normal distributions. Comparison with a dynamical simulation of soft spheres with diameters matched to the Volvox samples, and a weak long-range attractive force, show that…
Hard spheres with a polydispersity above approximately 8% are shown to crystallise into two phase-separated solid phases. A polydispersity above 8% is too large to be tolerated by a single solid phase but phase separation produces two fractions with polydispersities sufficiently narrow to allow them to crystallise. It may not be possible to observe this in experiment due to the intervention of a glass transition.
Shear viscosity and wall slip of dense suspensions of a silicone polymer incorporated with polydisperse particles were investigated. Three types of particles with low aspect ratios were used to achieve a relatively high maximum packing fraction of 0.86. Such a high maximum packing fraction allowed the preparation of suspensions with a wide range of solid volume fractions in the range of 0.62 to 0.82. The wall slip velocities of the suspensions in steady torsional and capillary flows were characterized and determined to be fully consistent with the mechanism of apparent slip layer formation at …
A theoretical scheme for the calculation of the full phase diagram (including cloud and shadow curves, binodals and distribution functions of the coexisting phases) for colloid-polymer mixtures with polymer chain length polydispersity and hard-sphere colloidal and polymeric monomer sizes polydispersity is proposed. The scheme combines thermodynamic perturbation theory for associating fluids and recently developed method used to determine the phase diagram of polydisperse spherical shape colloidal fluids (L.Bellier-Castella {\it et al.}, {\it J.Chem.Phys.} {\bf 113}, 8337(2000)). By way of illu…
In a previous paper (J. Zhang {\it et al.}, J. Chem. Phys. {\bf 110}, 5318 (1999)) we introduced a model for polydisperse hard sphere mixtures that is able to adjust its particle-size distribution. Here we give the explanation of the questions that arose in the previous description and present a consistent theory of the phase transition in this system, based on the Percus-Yevick equation of state. The transition is continuous, and like Bose-Einstein condensation a macroscopic aggregate is formed due to the microscopic interactions. A BMCSL-like treatment leads to the same conclusion with sligh…
Slow dynamics in a fluid are studied in one of the most basic systems possible: polydisperse hard spheres. Monodisperse hard spheres cannot be studied as the slow down in dynamics as the density is increased is preempted by crystallisation. As the dynamics slow they become more heterogeneous, the spread in the distances traveled by different particles in the same time increases. However, the dynamics appears to be less heterogeneous than in hard-sphere-like colloids at the same volume fraction. The particles which move least far in a characteristic relaxation time and, particularly, the partic…
It has been shown by Stell [J. Stat. Phys. 63, 1203 (1991)] that at low temperature monodisperse sticky spheres collapse to form coexisting close-packed solid and infinitely dilute gases. We show that polydisperse sticky spheres also collapse and calculate the collapse temperature. The polydisperse spheres separate into fractions with narrower polydispersities which can then solidify. This is the first example of a single-peaked polydisperse mixture phase separating. It implies that a mixture of polydisperse large hard spheres with much smaller hard spheres does not show fluid--fluid coexisten…
Using confocal microscopy we investigate the effect of attraction on the packing of polydisperse emulsions under gravity. We find that the distributions of neighbors, coordination number, and local packing fraction as a function of attraction are captured by recently proposed geometrical modeling and statistical mechanics approaches to granular matter. This extends the range of applicability of these tools to polydisperse, attractive jammed packings. Furthermore, the dependence of packing density and average coordination number on the strength of attraction provides the first experimental test…
Polydisperse mixtures are those in which components with a whole range of sizes are present. It is shown that the fluid phase of polydisperse hard spheres is thermodynamically unstable unless the density of large spheres decreases at least exponentially as their size increases. The instability is with respect to the large spheres crystallising out into multiple solid phases.
The most efficient way to pack equally sized spheres isotropically in 3D is known as the random close packed state, which provides a starting point for many approximations in physics and engineering. However, the particle size distribution of a real granular material is never monodisperse. Here we present a simple but accurate approximation for the random close packing density of hard spheres of any size distribution, based upon a mapping onto a one-dimensional problem. To test this theory we performed extensive simulations for mixtures of elastic spheres with hydrodynamic friction. The simula…
We study numerically the crystallization of a hard-sphere mixture with 8\% polydispersity. Although often used as a model glass former, for small system sizes we observe crystallization in molecular dynamics simulations. This opens the possibility to study the competition between crystallization and structural relaxation of the melt, which typically is out of reach due to the disparate timescales. We quantify the dependence of relaxation and crystallization times on density and system size. For one density and system size we perform a detailed committor analysis to investigate the suitability …
We use confocal microscopy to study a random close packed sample of colloidal particles. We introduce an algorithm to estimate the size of each particle. Taking into account their sizes, we compute the compressibility of the sample as a function of wave vector $q$, and find that this compressibility vanishes linearly as $q \rightarrow 0$. The particle sizes must be considered to calculate the compressibility properly. These results also suggest that the experimental packing is hyperuniform.
A new Monte Carlo approach is proposed to investigate the fluid-solid phase transition of the polydisperse system. By using the extended ensemble, a reversible path was constructed to link the monodisperse and corresponding polydisperse system. Once the fluid-solid coexistence point of the monodisperse system is known, the fluid-solid coexistence point of the polydisperse system can be obtained from the simulation. The validity of the method is checked by the simulation of the fluid-solid phase transition of a size-polydisperse hard sphere colloid. The results are in agreement with the previou…
We study the effects of size polydispersity on the gas-liquid phase behaviour of mixtures of sticky hard spheres. To achieve this, the system of coupled quadratic equations for the contact values of the partial cavity functions of the Percus-Yevick solution is solved within a perturbation expansion in the polydispersity, i.e. the normalized width of the size distribution. This allows us to make predictions for various thermodynamic quantities which can be tested against numerical simulations and experiments. In particular, we determine the leading-order effects of size polydispersity on the cl…
We study the phase behavior of mixtures of monodisperse colloidal spheres with a depletion agent which can have arbitrary shape and can possess a polydisperse size or shape distribution. In the low concentration limit, considered here, we can employ the free-volume theory and take the geometry of particles of the depletion agent into account within the framework of fundamental measure theory. We apply our approach to study the phase diagram of a mixture of (monodisperse) colloidal spheres and two polydisperse polymer components. By fine tuning the distribution of the polymer it is possible to …
A recent proposal in which the equation of state of a polydisperse hard-sphere mixture is mapped onto that of the one-component fluid is extrapolated beyond the freezing point to estimate the jamming packing fraction $ϕ_\text{J}$ of the polydisperse system as a simple function of $M_1M_3/M_2^2$, where $M_k$ is the $k$th moment of the size distribution. An analysis of experimental and simulation data of $ϕ_\text{J}$ for a large number of different mixtures shows a remarkable general agreement with the theoretical estimate. To give extra support to the procedure, simulation data for seventeen mi…
We propose an extension of the second-order Barker-Henderson perturbation theory for polydisperse hard-sphere multi-Morse mixture. To verify the accuracy of the theory, we compare its predictions for the limiting case of monodisperse system, with predictions of the very accurate reference hypernetted chain approximation. The theory is used to describe the liquid-gas phase behavior of the mixture with different type and different degree of polydispersity. In addition to the regular liquid-gas critical point, we observe the appearance of the second critical point induced by polydispersity. With …
The solid-solid coexistence of a polydisperse hard sphere system is studied by using the Monte Carlo simulation. The results show that for large enough polydispersity the solid-solid coexistence state is more stable than the single-phase solid. The two coexisting solids have different composition distributions but the same crystal structure. Moreover, there is evidence that the solid-solid transition terminates in a critical point as in the case of the fluid-fluid transition.
The fluid - crystal equilibria of polydisperse mixtures of hard spheres have been studied by computer simulation of the solid phase and using an accurate equation of state for the fluid. A new scheme has been developed to evaluate the composition of crystalline phases in equilibrium with a given polydisperse fluid. Some common assumptions in theoretical approaches and their results are discussed on the light of the simulation results. Finally, no evidence of the existence of a terminal polydispersity in the fluid phase is found for polydisperse hard spheres, the disagreement of this finding wi…
Phase behavior of the Yukawa hard-sphere polydisperse mixture with high degree of polydispersity is studied using high temperature approximation (HTA) and mean spherical approximation (MSA). We have extended and applied the scheme developed to calculate the phase diagrams of polydisperse mixtures described by the truncatable free energy models, i.e., the models with Helmholtz free energy defined by the finite number of the moments of the species distribution function. At high degree of polydispersity, several new features in the topology of the two-phase diagram have been observed: the cloud a…
We use specialized Monte Carlo simulation methods and moment free energy calculations to provide conclusive evidence that dense polydisperse spheres at equilibrium demix into coexisting fcc phases, with more phases appearing as the spread of diameters increases. We manage to track up to four coexisting phases. Each of these is fractionated: it contains a narrower distribution of particle sizes than is present in the system overall. We also demonstrate that, surprisingly, demixing transitions can be nearly continuous, accompanied by fluctuations in local particle size correlated over many latti…
The structure of polydisperse hard sphere fluids, in the presence of a wall, is studied by the Rosenfeld density functional theory. Within this approach, the local excess free energy depends on only four combinations of the full set of density fields. The case of continuous polydispersity thereby becomes tractable. We predict, generically, an oscillatory size segregation close to the wall, and connect this, by a perturbation theory for narrow distributions, with the reversible work for changing the size of one particle in a monodisperse reference fluid.
A model polydisperse fluid represents many real fluids such as colloidal suspensions and polymer solutions. In this study, considering a concentrated size-polydisperse hard sphere fluid with size derived from two different distribution functions, namely, uniform and Gaussian and explore the effect of polydispersity and mass scaling on the transport properties in general. A simple analytical solution based on the Boltzmann transport equation is also presented (together with the solution using Chapman-Enskog (CE) method) using which various transport coefficients are obtained. The central idea o…
The influence of packing protocol, size ratio, and pore structure on fractal exponents in dense polydisperse packings
Joint Institute for Nuclear Research（俄罗斯联邦杜布纳联合核子研究所）；Dokuchaev Soil Science Institute（多卡恰耶夫土壤科学研究所）；Horia Hulubei National Institute of Physics and Nuclear Engineering（霍里亚·胡利贝伊国家物理与核工程研究所）；Craiova University（克赖奥瓦大学）
A theoretical model for polydisperse systems of hard spheres is said to be truncatable when the excess free energy depends on the size distribution through a finite number $K$ of moments. This Note proves an exact scaling relation for truncatable free energies, which allows to reduce the effective degrees of freedom to $K-2$ independent combinations of the moments.
The effect of polydispersity on the freezing transition of hard spheres is examined within a moment description. At low polydispersities a single fluid-to-crystal transition is recovered. With increasing polydispersity we find a density above which the crystal melts back into an amorphous phase. The range of densities over which the crystalline phase is stable shrinks with increasing polydispersity until, at a certain level of polydispersity, the crystal disappears completely from the equilibrium phase diagram. The two transitions converge to a single point which we identify as the polydispers…
The phase diagram of a polydisperse hard sphere system is examined by numerical minimization of a discretized form of the Ramakrishnan-Yussouff free energy functional. Crystalline and glassy local minima of the free energy are located and the phase diagram in the density-polydispersity plane is mapped out by comparing the free energies of different local minima. The crystalline phase disappears and the glass becomes the equilibrium phase beyond a "terminal" value of the polydispersity. A crystal to glass transition is also observed as the density is increased at high polydispersity. The phase …
Unlike atoms, colloidal particles are not identical, but can only be synthesised within a finite size tolerance. Colloids are therefore polydisperse, i.e. mixtures of infinitely many components with sizes drawn from a continuous distribution. We model the crystallisation of hard-sphere colloids (with/without attractions) from an initially amorphous phase. Though the polydisperse hard-sphere phase diagram has been widely studied, it is not straightforwardly applicable to real colloidal crystals, since they are inevitably out of equilibrium. The process by which colloidal crystals form determine…
Particle size polydispersity can help to inhibit crystallization of the hard-sphere fluid into close-packed structures at high packing fractions and thus is often employed to create model glass-forming systems. Nonetheless, it is known that hard-sphere mixtures with modest polydispersity still have ordered ground states. Here, we demonstrate by computer simulation that hard-sphere mixtures with increased polydispersity fractionate on the basis of particle size, and a bimodal subpopulation favors formation of topologically close-packed C14 and C15 Laves phases in coexistence with a disordered p…
It is presented a numerical study on the unjamming packing fraction of bi- and polydisperse disk packings, which are generated through compression of a monodisperse crystal. In bidisperse systems, a fraction f_+ = 40% up to 80% of the total number of particles have their radii increased by ΔR, while the rest has their radii decreased by the same amount. Polydisperse packings are prepared by changing all particle radii according to a uniform distribution in the range [-ΔR,ΔR]. The results indicate that the critical packing fraction is never larger than the value for the initial monodisperse cry…
We analyze the slow, glassy structural relaxation as measured through collective and tagged-particle density correlation functions obtained from Brownian dynamics simulations for a polydisperse system of quasi-hard spheres in the framework of the mode-coupling theory of the glass transition (MCT). Asymptotic analyses show good agreement for the collective dynamics when polydispersity effects are taken into account in a multi-component calculation, but qualitative disagreement at small $q$ when the system is treated as effectively monodisperse. The origin of the different small-$q$ behaviour is…
Standard algorithms for the numerical integration of the Langevin equation require that interactions are slowly varying during to the integration timestep. This in not the case for hard-body systems, where there is no clearcut between the correlation time of the noise and the timescale of the interactions. Starting from a short time approximation of the Smoluchowsky equation, we introduce an algorithm for the simulation of the overdamped Brownian dynamics of polydisperse hard-spheres in absence of hydrodynamics interactions and briefly discuss the extension to the case of external drifts.
The phase diagram of soft spheres with size dispersion has been studied by means of an optimized Monte Carlo algorithm which allows to equilibrate below the kinetic glass transition for all sizes distribution. The system ubiquitously undergoes a first order freezing transition. While for small size dispersion the frozen phase has a crystalline structure, large density inhomogeneities appear in the highly disperse systems. Studying the interplay between the equilibrium phase diagram and the kinetic glass transition, we argue that the experimentally found terminal polydispersity of colloids is a…
We study the theoretical phase behavior of an asymmetric binary mixture of hard spheres, of which the smaller component is monodisperse and the larger component is polydisperse. The interactions are modelled in terms of the second virial coefficient and are assumed to be additive hard sphere interactions. The polydisperse component is subdivided into sub-components and has an average size ten times the size of the monodisperse component. We give the set of equations that defines the phase diagram for mixtures with more than two components in a solvent. We calculate the theoretical liquid-liqui…
The liquid-gas phase diagram for polydisperse dipolar hard-sphere fluid with polydispersity in the hard-sphere size and dipolar moment is calculated using extension of the recently proposed thermodynamic perturbation theory for central force (TPT-CF) associating potential. To establish the connection with the phase behavior of ferrocolloidal dispersions it is assumed that the dipole moment is proportional to the cube of the hard-sphere diameter. We present and discuss the full phase diagram, which includes cloud and shadow curves, binodals and distribution functions of the coexisting daughter …
We discuss phase coexistence of polydisperse colloidal suspensions in the presence of adhesion forces. The combined effect of polydispersity and Baxter's sticky-hard-sphere (SHS) potential, describing hard spheres interacting via strong and very short-ranged attractive forces, give rise, within the Percus-Yevick (PY) approximation, to a system of coupled quadratic equations which, in general, cannot be solved either analytically or numerically. We review and compare two recent alternative proposals, which we have attempted to by-pass this difficulty. In the first one, truncating the density ex…
An analytic derivation of the spinodal of a polydisperse mixture is presented. It holds for fluids whose excess free energy can be accurately described by a function of a few moments of the size distribution. It is shown that one such mixture of hard spheres in the Percus-Yevick approximation never demixes, despite its size distribution. In the Boublik-Mansoori-Carnahan-Starling-Leland approximation, though, it demixes for a sufficiently wide log-normal size distribution. The importance of this result is twofold: first, this distribution is unimodal, and yet it phase separates; and second, log…
Computer simulations give precious insight into the microscopic behavior of supercooled liquids and glasses, but their typical time scales are orders of magnitude shorter than the experimentally relevant ones. We recently closed this gap for a class of models of size polydisperse fluids, which we successfully equilibrate beyond laboratory time scales by means of the swap Monte Carlo algorithm. In this contribution, we study the interplay between compositional and geometric local orders in a model of polydisperse hard spheres equilibrated with this algorithm. Local compositional order has a wea…
