Entropy of jammed matter

We investigate the nature of randomness in disordered packings of frictional spheres. We calculate the entropy of 3D packings through the force and volume ensemble of jammed matter, a mesoscopic ensemble and numerical simulations using volume fluctuation analysis and graph theoretical methods. Equations of state are obtained relating entropy, volume fraction and compactivity characterizing the different states of jammed matter. At the mesoscopic level the entropy vanishes at random close packing, while the microscopic states contribute to a finite entropy. The entropy of the jammed system reveals that the random loose packings are more disordered than random close packings, allowing for an unambiguous interpretation of both limits.     

Jamming II: Edwards’ statistical mechanics of random packings of hard spheres

The problem of finding the most efficient way to pack spheres has an illustrious history, dating back to the crystalline arrays conjectured by Kepler and the random geometries explored by Bernal in the 1960s. This problem finds applications spanning from the mathematician’s pencil, the processing of granular materials, the jamming and glass transitions, all the way to fruit packing in every grocery. There are presently numerous experiments showing that the loosest way to pack spheres gives a density of ∼55% (named random loose packing, RLP) while filling all the loose voids results in a maximum density of ∼63%-64% (named random close packing, RCP). While those values seem robustly true, to this date there is no well-accepted physical explanation or theoretical prediction for them. Here we develop a common framework for understanding the random packings of monodisperse hard spheres whose limits can be interpreted as the experimentally observed RLP and RCP. The reason for these limits arises from a statistical picture of jammed states in which the RCP can be interpreted as the ground state of the ensemble of jammed matter with zero compactivity, while the RLP arises in the infinite compactivity limit. We combine an extended statistical mechanics approach ‘a la Edwards’ (where the role traditionally played by the energy and temperature in thermal systems is substituted by the volume and compactivity) with a constraint on mechanical stability imposed by the isostatic condition. We show how such approaches can bring results that can be compared to experiments and allow for an exploitation of the statistical mechanics framework. The key result is the use of a relation between the local Voronoi volumes of the constituent grains (denoted the volume function) and the number of neighbors in contact that permits us to simply combine the two approaches to develop a theory of volume fluctuations in jammed matter. Ultimately, our results lead to a phase diagram that provides a unifying view of the disordered hard sphere packing problem and further sheds light on a diverse spectrum of data, including the RLP state. Theoretical results are well reproduced by numerical simulations that confirm the essential role played by friction in determining both the RLP and RCP limits. The RLP values depend on friction, explaining why varied experimental results can be obtained.     

Jamming in two-dimensional packings

We investigate the existence of random close and random loose packing limits in two-dimensional packings of monodisperse hard disks. A statistical mechanics approach-based on several approximations to predict the probability distribution of volumes-suggests the existence of the limiting densities of the jammed packings according to their coordination number and compactivity. This result has implications for the understanding of disordered states in the disk packing problem as well as the existence of a putative glass transition in two-dimensional systems.     

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.     

Structural transitions in granular packs: statistical mechanics and statistical geometry investigations

We investigate equal spheres packings generated from several experiments and from a large number of different numerical simulations. The structural organization of these disordered packings is studied in terms of the network of common neighbours. This geometrical analysis reveals sharp changes in the network’s clustering occurring at the packing fractions (fraction of volume occupied by the spheres respect to the total volume, ρ) corresponding to the so called Random Loose Packing limit (RLP, ρ ～ 0.555) and Random Close Packing limit (RCP, ρ ～ 0.645). At these packing fractions we also observe abrupt changes in the fluctuations of the portion of free volume around each sphere. We analyze such fluctuations by means of a statistical mechanics approach and we show that these anomalies are associated to sharp variations in a generalized thermodynamical variable which is the analogous for these a-thermal systems to the specific heat in thermal systems.     

Is random close packing of spheres well defined?

Despite its long history, there are many fundamental issues concerning random packings of spheres that remain elusive, including a precise definition of random close packing (RCP). We argue that the current picture of RCP cannot be made mathematically precise and support this conclusion via a molecular dynamics study of hard spheres using the Lubachevsky-Stillinger compression algorithm. We suggest that this impasse can be broken by introducing the new concept of a maximally random jammed state, which can be made precise.     

Jamming I: A volume function for jammed matter

We introduce a “Hamiltonian”-like function, called the volume function, indispensable to describe the ensemble of jammed matter such as granular materials and emulsions from a geometrical point of view. The volume function represents the available volume of each particle in the jammed systems. At the microscopic level, we show that the volume function is the Voronoi volume associated to each particle and in turn we provide an analytical formula for the Voronoi volume in terms of the contact network, valid for any dimension. We then develop a statistical theory for the probability distribution of the volumes in 3d to calculate an average volume function coarse-grained at a mesoscopic level. The salient result is the discovery of a mesoscopic volume function inversely proportional to the coordination number. Our analysis is the first step toward the calculation of macroscopic observables and equations of state using the statistical mechanics of jammed matter, when supplemented by the condition of mechanical equilibrium of jamming that properly defines jammed matter at the ensemble level.     

Effective temperature and jamming transition in dense, gently sheared granular assemblies

We present extensive computational results for the effective temperature, defined by the fluctuation-dissipation relation between the mean square displacement and the average displacement of grains, under the action of a weak, external perturbation, of a sheared, bi-disperse granular packing of compressible spheres. We study the dependence of this parameter on the shear rate and volume fractions, the type of particle and the observable in the fluctuation-dissipation relation. We find the same temperature for different tracer particles in the system. The temperature becomes independent on the shear rate for slow enough shear suggesting that it is the effective temperature of the jammed packing. However, we also show that the agreement of the effective temperature for different observables is only approximate, for very long times, suggesting that this defintion may not capture the full thermodynamics of the system. On the other hand, we find good agreement between the dynamical effective temperature and a compactivity calculated assuming that all jammed states are equiprobable. Therefore, this definition of temperature may capture an instance of the ergodic hypothesis for granular materials as proposed by theoretical formalisms for jamming. Finally, our simulations indicate that the average shear stress and apparent shear viscosity follow the usual relation with the shear rate for complex fluids. Our results show that the application of shear induces jamming in packings whose particles interact by tangential forces.     

On the existence of stationary states during granular compaction

When submitted to gentle mechanical taps a granular packing slowly compacts until it reaches a stationary state that depends on the tap characteristics. The properties of such stationary states are experimentally investigated. The influence of the initial state, taps properties and tapping protocol are studied. The compactivity of the packings is determinated. Our results strongly support the idea that the stationary states are genuine thermodynamic states.     

Do binary hard disks exhibit an ideal glass transition?

We demonstrate that there is no ideal glass transition in a binary hard-disk mixture by explicitly constructing an exponential number of jammed packings with densities spanning the spectrum from the accepted amorphous glassy state to the phase-separated crystal. Thus the configurational entropy cannot be zero for an ideal amorphous glass, presumed distinct from the crystal in numerous theoretical and numerical estimates in the literature. This objection parallels our previous critique of the idea that there is a most-dense random (close) packing for hard spheres [Torquato, Phys. Rev. Lett. 84, 2064 (2000)10.1103/PhysRevLett.84.2064].     

Brownian dynamics of polydisperse colloidal hard spheres: Equilibrium structures and random close packings

Recently we presented a new technique for numerical simulations of colloidal hard-sphere systems and showed its high efficiency. Here, we extend our calculations to the treatment of both 2- and 3-dimensional monodisperse and 3-dimensional polydisperse systems (with sampled finite Gaussian size distribution of particle radii), focusing on equilibrium pair distribution functions and structure factors as well as volume fractions of random close packing (RCP). The latter were determined using in principle the same technique as Woodcock or Stillinger had used. Results for the monodisperse 3-dimensional system show very good agreement compared to both pair distribution and structure factor predicted by the Percus-Yevick approximation for the fluid state (volume fractions up to 0.50). We were not able to find crystalline 3d systems at volume fractions 0.50–0.58 as shown by former simulations of Reeet al. or experiments of Pusey and van Megen, due to the fact that we used random start configurations and no constraints of particle positions as in the cell model of Hoover and Ree, and effects of the overall entropy of the system, responsible for the melting and freezing phase transitions, are neglected in our calculations. Nevertheless, we obtained reasonable results concerning concentration-dependent long-time selfdiffusion coefficients (as shown before) and equilibrium structure of samples in the fluid state, and the determination of the volume fraction of random close packing (RCP, glassy state). As expected, polydispersity increases the respective volume fraction of RCP due to the decrease in free volume by the fraction of the smaller spheres which fill gaps between the larger particles.     

Geometric partition functions of cellular systems: Explicit calculation of the entropy in two and three dimensions

A method is proposed for the characterisation of the entropy of cellular structures, based on the compactivity concept for granular packings. Hamiltonian-like volume functions are constructed both in two and in three dimensions, enabling the identification of a phase space and making it possible to take account of geometrical correlations systematically. Case studies are presented for which explicit calculations of the mean vertex density and porosity fluctuations are given as functions of compactivity. The formalism applies equally well to two- and three-dimensional granular assemblies.     

Dense and nearly jammed random packings of freely jointed chains of tangent hard spheres

Dense packings of freely jointed chains of tangent hard spheres are produced by a novel Monte Carlo method. Within statistical uncertainty, chains reach a maximally random jammed (MRJ) state at the same volume fraction as packings of single hard spheres. A structural analysis shows that as the MRJ state is approached (i) the radial distribution function for chains remains distinct from but approaches that of single hard sphere packings quite closely, (ii) chains undergo progressive collapse, and (iii) a small but increasing fraction of sites possess highly ordered first coordination shells.     

Role of interparticle forces in the formation of random loose packing

We present a physical and numerical study of the settling of uniform spheres in liquids and show that interparticle forces play a critical role in forming the so-called random loose packing (RLP). Different packing conditions give different interparticle forces and, hence, different RLP. Two types of interparticle forces are identified: process dependent and process independent. The van der Waals force, as the major cohesive force in the present study, plays a critical role in effecting the process-dependent forces such as drag and lift forces. An equation is formulated to describe the relationship between the macroscopic packing fraction and microscopic interparticle forces in a packing. We argue there is no lowest packing fraction for a mechanically stable RLP; hence, the packing fractions of RLP can range from 0 to 0.64 depending on the cohesive and frictional conditions between particles.     

Onset of mechanical stability in random packings of frictional spheres

Using sedimentation to obtain precisely controlled packings of noncohesive spheres, we find that the volume fraction phiRLP of the loosest mechanically stable packing is in an operational sense well defined by a limit process. This random loose packing volume fraction decreases with decreasing pressure p and increasing interparticle friction coefficient mu. Using x-ray tomography to correct for a container boundary effect that depends on particle size, we find for rough particles in the limit p-->0 a new lower bound, phiRLP=0.550+/-0.001.     

Packing of compressible granular materials

3D computer simulations and experiments are employed to study random packings of compressible spherical grains under external confining stress. In the rigid ball limit, we find a continuous transition in which the stress vanishes as (straight phi-straight phi(c))(beta), where straight phi is the (solid phase) volume density. The value of straight phi(c) depends on whether the grains interact via only normal forces (giving rise to random close packings) or by a combination of normal and friction generated transverse forces (producing random loose packings). In both cases, near the transition, the system's response is controlled by localized force chains.     

Dense packing in the monodisperse hard-sphere system: A numerical study

We report a numerical study of the close packing of monodisperse hard spheres. The close packings of hard spheres are produced by the Lubachesky-Stillinger (LS) compression algorithm and span the range from the disordered states to the ordered states. We provide quantitative evidence for the claim that the density and structural order of the arrested close packing can be determined by the compression rate, i.e., with slower rates producing denser and more ordered structures. Through deeply analyzing the structure of the resulting arrested close packings, a transition region has been identified in the plane of density and reciprocal compression rate, in between what have been historically thought of as amorphous and crystalline packings. We also find clear system size dependences in studying the structural properties of the packings from the disordered ones to the ordered ones. These detailed investigations, on the structure of the arrested close packings, may provide a link between the glassy states and the crystalline states in the hard spheres.     

Discrete Element Method studies of the collision of one rapid sphere on 2D and 3D packings

We performed numerical simulations of one-bead collision on the surface of a static granular medium. The simulations have been done for two- and three-dimensional packings of beads. The effect of the incident bead velocity, the shot angle, the mechanical parameters and the packing structure are analyzed for ordered and disordered 2D packings and only disordered 3D packings. The 2D results are in good agreement with experimental available data. The 3D simulations give good preliminaries results about the shock-wave propagation through the stacking and provides new insights in the ejection process (“splash function”).     

New jamming scenario: from marginal jamming to deep jamming

We study the properties of jammed packings of frictionless spheres over a wide range of volume fractions. There exists a crossover volume fraction which separates deeply jammed solids from marginally jammed solids. In deeply jammed solids, all the scalings presented in marginally jammed solids are replaced with remarkably different ones with potential independent exponents. Correspondingly, there are structural changes in the pair distribution function associated with the crossover. The normal modes of vibration of deeply jammed solids also exhibit some anomalies, e.g., strengthened quasilocalization and the absence of Debye-like density of states at low frequencies. Deeply jammed systems may thus be cataloged to a new class of amorphous solids.     

Why is random close packing reproducible?

We link the thermodynamics of colloidal suspensions to the statistics of regular and random packings. Random close packing has defied a rigorous definition yet, in three dimensions, there is near universal agreement on the volume fraction at which it occurs. We conjecture that the common value of phi{rcp} approximately 0.64 arises from a divergence in the rate at which accessible states disappear. We relate this rate to the equation of state for a hard-sphere fluid on a metastable, noncrystalline branch.