A model for the packing of irregularly shaped grains

In this paper we will attempt to address the problem of the packing properties of granular materials composed of irregularly shaped grains (using configurational statistical mechanics). In particular, we will develop a model for a system of irregular grains based upon perturbing a packing of mono- or poly-disperse spheres. In the mono-disperse case we will show that the system packs less densely than a packing of perfect spheres, except when local correlations between configurations of grains are taken into account. The opposite is found to be true for a perturbation expansion based upon poly-disperse spheres. Finally we will show that for a bi-disperse packing of spheres phase segregation occurs for any size ratio and discuss whether this is to be expected.     

The Effect of Sphere Size on the Phase Behaviors in the Rod and Sphere Mixture System

The addition of polysaccharides, such as chondroitin sulfate (Chs), to the aqueous suspension of tobacco mosaic virus (TMV) results in the TMV aggregation at very dilute TMV concentration compared with the addition of polyethylene oxide (PEO). The Chs chain has a semirigid nature, whereas the PEO has a flexible nature. In this study, we investigated the effect of the size of spherical polymer coils on the phase behaviors in the mixtures of rods and spheres using Monte Carlo simulations. As a model for TMV, we used the spherocylinder particle. The Chs and PEO chains were simplified to spherical particles having different sizes. With the addition of large spherical particles, the system changed from miscible phase to isotropic–isotropic phase separation and then isotropic–nematic phase separation states, whereas with the addition of small spherical particles, the system transformed from miscible isotropic phase to miscible nematic phase. We found that the sphere size had an important influence on the phase behaviors in the mixtures of rods and spheres.     

Phase behavior of binary hard-sphere mixtures from perturbation theory

Using a first-order perturbation theory, we have studied the phase diagram of a binary mixture of hard spheres for different values of the size ratio. Recent models for the two-body depletion potential between large spheres are used to take into account the role of the small spheres. The theory predicts a complex phase diagram including a fluid-solid transition at high packing fraction of small spheres, metastability of fluid-fluid demixing, an isostructural solid-solid transition at high packing fraction of the large spheres for sufficiently small values of the size ratio q of the spheres, and the tendency to sticky-sphere behavior in the limit q-->0. The agreement with recent simulation results is quite good. We also show that this phenomenology was already implicit in the pioneering work of Asakura and Oosawa.     

Depletion forces and packing models

In binary colloidal suspensions, due to the depletion forces, large spheres tend to pack together so as to make entropy maximum. Based on the complexities of depletion forces and phase behaviors in binary mixtures, two packing models, named nucleation and non-nucleation packing, are proposed in this Letter. Numerical results show that, when the volume fraction is small, the nucleation is possible. As a result, the large spheres tend to pack into a larger and larger cluster. However, when the volume fraction is very large in a way, the hard-spheres will proceed in the non-nucleation packing fashion. The numerical results also show that differences between the two packing models decrease with the decrease of volume fraction.     

Self-diffusion and sedimentation of tracer spheres in (semi)dilute dispersions of rigid colloidal rods

Long-time self-diffusion and sedimentation of fluorescent tracer spheres in electrostatically stabilized dispersions of rigid colloidal host rods have been measured in situ with fluorescence recovery after photobleaching, and gravitational and ultracentrifugal sedimentation. The dynamics of silica tracer spheres of 39 and 370 nm radius was monitored in dispersions of host rods with aspect ratios 9.6 and 25.7 at various rod volume fractions. The translational and rotational diffusion coefficient of the host rods was obtained independently with dynamic light scattering and birefringence decay measurements. Our results indicate that sedimentation and long-time self-diffusion are determined by the same friction factor. Furthermore we find that, as long as the host rods are relatively mobile, tracer sphere sedimentation and long-time self-diffusion are governed by the macroscopic solution viscosity, regardless of the tracer and host rod size. However, when the host rods are immobilized, due to rod entanglements at higher volume fractions, tracer sphere dynamics depends strongly on the tracer size relative to the pore size of the host rod network. The large tracers are completely trapped in the network whereas the small tracer spheres remain mobile. Current models for tracer sphere motion in rod assemblies do not satisfactorily explain the complete dynamic regime covered by our experimental model system because the effect of host rod mobility is not properly taken into account.     

Depletion effects in smectic phases of hard-rod-hard-sphere mixtures

It is known that when hard spheres are added to a pure system of hard rods the stability of the smectic phase may be greatly enhanced, and that this effect can be rationalised in terms of depletion forces. In the present paper we first study the effect of orientational order on depletion forces in this particular binary system, comparing our results with those obtained adopting the usual approximation of considering the rods parallel and their orientations frozen. We consider mixtures with rods of different aspect ratios and spheres of different diameters, and we treat them within Onsager theory. Our results indicate that depletion effects, and consequently smectic stability, decrease significantly as a result of orientational disorder in the smectic phase when compared with corresponding data based on the frozen-orientation approximation. These results are discussed in terms of the τ parameter, which has been proposed as a convenient measure of depletion strength. We present closed expressions for τ, and show that it is intimately connected with the depletion potential. We then analyse the effect of particle geometry by comparing results pertaining to systems of parallel rods of different shapes (spherocylinders, cylinders and parallelepipeds). We finally provide results based on the Zwanzig approximation of a fundamental-measure density-functional theory applied to mixtures of parallelepipeds and cubes of different sizes. In this case, we show that the τ parameter exhibits a linear asymptotic behaviour in the limit of large values of the hard-rod aspect ratio, in conformity with Onsager theory, as well as in the limit of large values of the ratio of rod breadth to cube side length, d, in contrast to Onsager approximation, which predicts τ ∼ d ³. Based on both this result and the Percus-Yevick approximation for the direct correlation function for a hard-sphere binary mixture in the same limit of infinite asymmetry, we speculate that, for spherocylinders and spheres, the τ parameter should be of order unity as d tends to infinity.     

受振颗粒“毛细”系统中的对流与有序化

将球形颗粒倒入内径较窄的管状容器时,管壁的曲率会对颗粒的堆积结构产生影响,存在壁效应. 实验表明通过连续的竖直方向的振动,壁效应可以被强化,颗粒可以经由对流由无序排列转变为稳定的同轴筒形“壳层”结构. 每一壳层内,颗粒是二维的六角密堆积, 在这一转变过程中,颗粒堆积率的径向分布由初始的衰减振荡转变为等幅振荡. 分析了堆积率的不均匀性及空气在对流中的作用,以及形成“壳层”结构的动力学过程,对“壳层”结构的稳定性亦进行了讨论. 关键词： 颗粒物质 对流 有序化 毛细     

Smectic phases in hard particle mixtures: Koda's theory

Mixtures of parallel linear particles and spheres tend to demix upon compression. The linear species usually concentrates in regular layers, thus forming a smectic phase. With increasing concentration of spheres this ‘smectic demixing’ transition occurs at ever lower packing densities. For the specific case of hard spherocylinders and spheres Koda et al. [T. Koda, M. Numajiri, S. Ikeda, J. Phys. Jap., 65, 3551 (1996)] have explained the layering effect in terms of a second virial approximation to the free energy. We extend this approach from spherocylinders to other linear particles, namely fused spheres, ellipsoids and sphero-ellipsoids.     

Polytetrahedral nature of the dense disordered packings of hard spheres

We study the structure of numerically simulated hard sphere packings at different densities by investigating local tetrahedral configurations of the spheres. Clusters of tetrahedra adjacent by faces present relatively dense aggregates of spheres atypical for crystals. The number of spheres participating in such polytetrahedral configurations increases with densification of the packing, and at the Bernal's limiting density (the packing fraction around 0.64) all spheres of the packing become involved in such tetrahedra. Thus the polytetrahedral packing cannot provide further increase in the density, and alternative structural change (formation of crystalline nuclei) begins henceforth.     

The effects of forcing and dissipation on phase transitions in thin granular layers

Recent experimental and computational studies of vibrated thin layers of identical spheres have shown transitions to ordered phases similar to those seen in equilibrium systems. Motivated by these results, we carry out simulations of hard inelastic spheres forced by homogenous white noise. We find a transition to an ordered state of the same symmetry as that seen in the experiments, but the clear phase separation observed in the vibrated system is absent. Simulations of purely elastic spheres also show no evidence for phase separation. We show that the energy injection in the vibrated system is dramatically different in the different phases, and suggest that this creates an effective surface tension not present in the equilibrium or randomly forced systems. We do find, however, that inelasticity suppresses the onset of the ordered phase with random forcing, as is observed in the vibrating system, and that the amount of the suppression is proportional to the degree of inelasticity. The suppression depends on the details of the energy injection mechanism, but is completely eliminated when inelastic collisions are replaced by uniform system-wide energy dissipation.     

球型和棒状金纳米粒子的光谱性质比较

柠檬酸钠还原和诱导晶种生长法合成了球型和棒状金纳米粒子。金纳米粒子的吸收光谱表明,表面等离子体共振(SPR)强烈依赖于金属粒子的形状,球型粒子表现为单-SPR谱峰,而棒状粒子则具有横向和纵向SPR谱峰,且纵向SPR峰位和强度取决于棒状粒子的径横比。棒状金纳米粒子对吸附的对巯基苯甲酸分子的拉曼散射比球型金纳米粒子具有更强的表面增强性能,归因于棒状粒子高能晶面上的吸附可能导致的更强的化学增强效应。     

The statistical mechanics of granular systems composed of elongated grains

In this paper we will suggest a model for the packing properties and phase behaviour of a granular material whose constituents are elongated in nature, using the concepts of configurational statistical mechanics. We will show that, depending upon the shape of the grains, the systems need not necessarily undergo a discontinuous first-order phase transition (even at minimum close packing). We will also briefly discuss the relationship between this model and more conventional models, such as Onsager's hard rod model.     

Non-crystalline structures in a Lennard-Jones potential

It is sometimes proposed that cunning packings of spheres could account for the structure of a metallic amorphous material. For such packings, relaxation is thought to result only in a small improvement of local distortions or stresses due to the building of the model, without changing much the radial distribution functions of the atoms.From this issue, it seems rather that any initial packing of spheres do reach (by relaxation in a Lennard-Jones potential) the f.c.c. structure or a reproducible “amorphous state”.     

A direct link between the lie group SU(3) and the singular hypersurface <Emphasis Type="Italic">X</Emphasis><Superscript>3</Superscript>+…=0 via quantum mechanics

A classical phase space with a suitable symplectic structure is constructed together with functions which have Possion brackets algebraically identical to the Lie algebra structure of the Lie group SU(3). It is shown that in this phase space there are two spheres which intersect at one point. Such a system has a representation as an algebraic curve of the form X ³+…=0 in C ³. The curve introduced is singular at the origin in the limit when the radii of the spheres go to zero. A direct connection between the Lie groups SU(3) and a singular curve in C ³ is thus established. The key step needed to do this was to treat the Lie group as a quantum system and determine its phase space.     

Self-assembly of particles for densest packing by mechanical vibration

It is shown that by properly controlling vibrational and charging conditions, the transition from disordered to ordered, densest packing of particles can be obtained consistently. The method applies to both spherical and nonspherical particles. For spheres, face centered cubic packing with different orientations can be achieved by monitoring the vibration amplitude and frequency, and the structure of the bottom layer, in particular. The resultant force structures are ordered but do not necessarily correspond to the packing structures fully. The implications of the findings are also discussed.     

Jamming III: Characterizing randomness via the entropy of jammed matter

The nature of randomness in disordered packings of frictional and frictionless spheres is investigated using theory and simulations of identical spherical grains. The entropy of the packings is defined through the force and volume ensemble of jammed matter and this is shown to be difficult to calculate analytically. A mesoscopic ensemble of isostatic states is then utilized in an effort to predict the entropy through the definition of a volume function that is dependent on the coordination number. Equations of state are obtained relating entropy, volume fraction and compactivity characterizing the different states of jammed matter, and elucidating the phase diagram for jammed granular matter. Analytical calculations are compared to numerical simulations using volume fluctuation analysis and graph theoretical methods, with reasonable agreement. The entropy of the jammed system reveals that random loose packings are more disordered than random close packings, allowing for an unambiguous interpretation of both limits. Ensemble calculations show that the entropy vanishes at random close packing (RCP), while numerical simulations show that a finite entropy remains in the microscopic states at RCP. The notion of a negative compactivity, which explores states with volume fractions below those achievable by existing simulation protocols, is also explored, expanding the equations of state. The mesoscopic theory reproduces the simulations results in shape well, though a difference in magnitude implies that the entire entropy of the packing may not be captured by the methods presented herein. We discuss possible extensions to the present mesoscopic approach describing packings from random loose packing (RLP) to RCP to the ordered branch of the equation of state in an effort to understand the entropy of jammed matter in the full range of densities from RLP to face-centered cubic (FCC) packing.     

Surface-induced first-order transition in athermal polymer-nanoparticle blends

We investigate the phase behavior of athermal polymer-nanoparticle blends near a substrate. We apply a recent fluids density functional theory of Tripathi and Chapman to a simple model of the blend as a mixture of hard spheres and freely jointed hard chains, near a hard wall. We find that there is a first-order phase transition in which the nanoparticles expel the polymer from the surface to form a monolayer. The nanoparticle transition density depends on the length of the polymer and the overall bulk density of the system. The effect is due both to packing entropy effects related to size asymmetry between the components and to the polymer configurational entropy. The simplicity of the system allows us to understand the so-called "entropic-push" observed in experiments.     

On hydraulic permeability of random packs of monodisperse spheres: Direct flow simulations versus correlations

Hydraulic permeability is studied in porous media consisting of randomly distributed monodisperse spheres by means of computational fluid dynamics (CFD) simulations. The packing of spheres is generated by inserting a certain number of nonoverlapping spherical particles inside a cubic box at both low and high packing fractions using proper algorithms. Fluid flow simulations are performed within the interparticulate porous space by solving Navier-Stokes equations in a low-Reynolds laminar flow regime. The hydraulic permeability is calculated from the Darcy equation once the mean values of velocity and pressure gradient are calculated across the particle packing. The simulation results for the pressure drop across the packing are verified by the Ergun equation for the lower range of porosities (<0.75), and the Stokes equation for higher porosities (∼1). Using the results of simulations, the effects of porosity and particle diameters on the hydraulic permeability are investigated. Simulations precisely specified the range of applicability of empirical or semi-empirical correlations for hydraulic permeability, namely the Carman-Kozeny, Rumpf-Gupte, and Howells-Hinch formulas. The number of spheres in the model is gradually decreased from 2000 to 20 to discover the finite-size effect of pores on the hydraulic permeability of spherical packing, which has not been clearly addressed in the literature. In addition, the scale dependence of hydraulic permeability is studied via simulations of the packing of spheres shrunk to lower scales. The results of this work not only reveal the validity range of the aforementioned correlations, but also show the finite-size effect of pores and the scale-independence of direct CFD simulations for hydraulic permeability.     

A first-order phase transition defines the random close packing of hard spheres

Randomly packing spheres of equal size into a container consistently results in a static configuration with a density of ∼64%. The ubiquity of random close packing (RCP) rather than the optimal crystalline array at 74% begs the question of the physical law behind this empirically deduced state. Indeed, there is no signature of any macroscopic quantity with a discontinuity associated with the observed packing limit. Here we show that RCP can be interpreted as a manifestation of a thermodynamic singularity, which defines it as the “freezing point” in a first-order phase transition between ordered and disordered packing phases. Despite the athermal nature of granular matter, we show the thermodynamic character of the transition in that it is accompanied by sharp discontinuities in volume and entropy. This occurs at a critical compactivity, which is the intensive variable that plays the role of temperature in granular matter. Our results predict the experimental conditions necessary for the formation of a jammed crystal by calculating an analogue of the “entropy of fusion”. This approach is useful since it maps out-of-equilibrium problems in complex systems onto simpler established frameworks in statistical mechanics.