We consider the link between fragility and elasticity that follows from analysis of the data for a set of soft-colloid materials consisting of deformable spheres reported by Mattsson et. al., in Nature vol 462, 83 (2009). Fragility index for a soft-colloid is obtained from the density dependence of the long time relaxation near a so-called glass transition point. In addition, we fit data for the high frequency shear modulus for the respective soft-colloid to a corresponding theoretical expression for the same modulus. This expression for the elastic constant is in terms of the corresponding pair correlation function for the liquid treated as of uniform density. The pair correlation function is adjusted through a proper choice of the parameters for the two body interaction potential for the respective soft-colloid material. The nature of correlation between the fragility and Poisson ratio observed for the soft colloids is qualitatively different, as compared to the same for molecular glasses. The observed link between fragility of a metastable liquid and its elastic coefficients is a manifestation of the effects of structure of the fluid on its dynamics.
We introduce the Poisson-Boltzmann cell model for spherical colloidal particles with a heterogeneous surface charge distribution. This model is obtained by generalizing existing cell models for mixtures of homogeneously charged colloidal spheres. Our new model has similar features as Onsager's second-virial theory for liquid crystals, but it predicts no orientational ordering if there is no positional ordering. This implies that all phases of heterogeneously charged colloids that are liquid-like with respect to translational degrees of freedom are also isotropic with respect to particle orient…
Within the framework of a Modified Poisson-Boltzmann theory accounting for steric effects of microions, we prove analytically that the effective pair interactions between like-charge colloids immersed in a confined electrolyte are repulsive. Our approach encompasses and extends previously known results to the case of complete confinement, and further incorporates the finite size of the microions which is absent in the standard Poisson-Boltzmann theory.
We study theoretically the osmotic pressure of a suspension of charged objects (e.g., colloids, polyelectrolytes, clay platelets, etc.) dialyzed against an electrolyte solution using the cell model and linear Poisson-Boltzmann (PB) theory. From the volume derivative of the grand potential functional of linear theory we obtain two novel expressions for the osmotic pressure in terms of the potential- or ion-profiles, neither of which coincides with the expression known from nonlinear PB theory, namely, the density of microions at the cell boundary. We show that the range of validity of lineariza…
The effective electrostatic interaction between a pair of colloids, both of them located close to each other at an electrolyte interface, is studied by employing the full, nonlinear Poisson-Boltzmann (PB) theory within classical density functional theory. Using a simplified yet appropriate model, all contributions to the effective interaction are obtained exactly, albeit numerically. The comparison between our results and those obtained within linearized PB theory reveals that the latter overestimates these contributions significantly at short inter-particle separations. Whereas the surface co…
We describe a method to simulate the dynamics of charged colloidal particles suspended in a liquid containing dissociated ions and salt ions. Regimes of prime current interest are those of large volume fraction of colloids, highly charged particles and low salt concentrations. A description which is tractable under these conditions is obtained by treating the small dissociated and salt ions as continuous fields, while keeping the colloidal macroions as discrete particles. For each spatial configuration of the macroions, the electrostatic potential arising from all charges in the system is dete…
The HNC Ornstein-Zernike integral equations are used to determine the properties of simple models of colloidal solutions where the colloids and ions are immersed in a solvent considered as a dielectric continuum and have a size ratio equal to 80 and a charge ratio varying between 1 and 4000. At an infinite dilution of colloids, the effective interactions between colloids and ions are determined for ionic concentrations ranging from 0.001 to 0.1 mol/l and compared to those derived from the Poisson-Boltzmann theory. At finite concentrations, we discuss on the basis of the HNC results the possibi…
In this work, we investigate the ageing behavior of soft glassy solids of aqueous suspension of laponite under shear flow. We observe that when an imposed time is normalized by a dominating relaxation time of the system, the rheological response at different ages shows superposition. Analysis of this behavior suggests that the structural evolution with age under a deformation field, as represented by the dependence of dominant relaxation mode on age, becomes weaker as the system becomes progressively less homogeneous due to enhanced attractive interactions caused by addition of salt. Creep-rec…
Microscopic relaxation timescales are estimated from the autocorrelation functions obtained by dynamic light scattering experiments for Laponite suspensions with different concentrations ($C_{L}$), added salt concentrations ($C_{S}$) and temperatures ($T$). It has been shown in an earlier work [Soft Matter, 10, 3292-3300 (2014)] that the evolutions of relaxation timescales of colloidal glasses can be compared with molecular glass formers by mapping the waiting time ($t_{w}$) of the former with the inverse of thermodynamic temperature ($1/T$) of the latter. In this work, the fragility parameter…
Sedimentation-diffusion equilibrium density profiles of suspensions of charge-stabilized colloids are calculated theoretically and by Monte Carlo simulation, both for a one-component model of colloidal particles interacting through pairwise screened-Coulomb repulsions and for a three-component model of colloids, cations, and anions with unscreened-Coulomb interactions. We focus on a state point for which experimental measurements are available [C.P. Royall et al., J. Phys.: Cond. Matt. {\bf 17}, 2315 (2005)]. Despite the apparently different picture that emerges from the one- and three-compone…
Soft materials, such as colloidal suspensions, polymer solutions, and biological systems, are typically multicomponent mixtures of macromolecules and simpler components (e.g., microions, monomers, solvent) that can assemble into complex structures spanning broad length and time scales. Many characteristic traits of soft matter, e.g., mechanical fragility, sensitivity to external influence, and tunable thermal and optical properties, emerge from a mingling of microscopic and mesoscopic constituents. Large asymmetries in size and charge between macromolecules and microscopic components often mak…
We propose a simple approximation scheme to compute the effective charge of highly charged colloids (spherical or cylindrical with infinite length). Within non-linear Poisson-Boltzmann theory, we start from an expression of the effective charge in the infinite dilution limit which is asymptotically valid for large salt concentrations; this result is then extended to finite colloidal concentration, approximating the salt partitioning effect which relates the salt content in the suspension to that of a dializing reservoir. This leads to an analytical expression of the effective charge as a funct…
Thermodynamic properties of charge-stabilised colloidal suspensions are commonly modeled by implementing the mean-field Poisson-Boltzmann (PB) theory within a cell model. This approach models a bulk system by a single macroion, together with counterions and salt ions, confined to a symmetrically shaped, electroneutral cell. While easing solution of the nonlinear PB equation, the cell model neglects microion-induced correlations between macroions, precluding modeling of macroion ordering phenomena. An alternative approach, avoiding artificial constraints of cell geometry, maps a macroion-microi…
In his Comment (cond-mat/0104060) to [Phys. Rev. E 60, 6530 (1999)], Mateescu shows that while the effective interactions remain repulsive when the specific size of the micro-ions is taken into account via a Modified Poisson-Boltzmann equation, a similar conclusion cannot be reached for the situation of complete lateral confinement. This point is correct but has already been considered in a more general study [Phys. Rev. E 62, R1465 (2000), where repulsion is generically obtained]; moreover, we argue that it illustrates the irrelevancy of the notion of pair potential in completely confined con…
We study the counterion distribution around a spherical macroion and its osmotic pressure in the framework of the recently developed Debye-H"uckel-Hole-Cavity (DHHC) theory. This is a local density functional approach which incorporates correlations into Poisson-Boltzmann theory by adding a free energy correction based on the One Component Plasma. We compare the predictions for ion distribution and osmotic pressure obtained by the full theory and by its zero temperature limit with Monte Carlo simulations. They agree excellently for weakly developed correlations and give the correct trend for s…
We report extensive numerical simulations of different models of 2D polymer rings with internal elasticity. We monitor the dynamical behavior of the rings as a function of the packing fraction, to address the effects of particle deformation on the collective response of the system. In particular, we compare three different models: (i) a recently investigated model [Gnan \& Zaccarelli, Nat. Phys. 15, 683 (2019)], where an inner hertzian field providing the internal elasticity acts on the monomers of the ring, (ii) the same model where the effect of such a field on the center of mass is balanced…
The electrostatic potential of a highly charged disc (clay platelet) in an electrolyte is investigated in detail. The corresponding non-linear Poisson-Boltzmann (PB) equation is solved numerically, and we show that the far-field behaviour (relevant for colloidal interactions in dilute suspensions) is exactly that obtained within linearized PB theory, with the surface boundary condition of a uniform potential. The latter linear problem is solved by a new semi-analytical procedure and both the potential amplitude (quantified by an effective charge) and potential anisotropy coincide closely withi…
We show that the first non-linear correction to the linearised Poisson-Boltzman n (or DLVO) theory of effective pair interactions between charge-stabilised, co lloidal particles near a charged wall leads to an attractive component of entro pic origin. The position and depth of the potential compare favourably with rec ent experimental measurements
The interaction between charged bodies in an ionic solution is a general problem in colloid physics and becomes a central topic in the study of biological systems where the electrostatic interaction between proteins, nucleic acids, membranes is involved. This problem is often described starting from the simple one-dimensional model of two parallel charged plates. Several different approaches to this problem exist, focusing on different features. In many cases, an intuitive expression of the pressure exerted on the plates is proposed, which includes an electrostatic plus an osmotic contribution…
The electrostatic interaction between two non-identical, moderately charged colloids situated in close proximity of each other at a fluid interface is studied. By resorting to a well-justified model system, this problem is analytically solved within the framework of linearized Poisson-Boltzmann (PB) density functional theory (DFT). The resulting interaction comprises a surface and a line part, both of which, as functions of the inter-particle separation, show a rich behavior including monotonic as well as non-monotonic variations. In almost all cases, these variations cannot be captured correc…
In this thesis, the electrostatic interaction between two chemically identical colloids, both carrying constant surface potential is studied in the limit of short inter-particle separation at the interface of two immiscible fluids. Using an appropriate model system, the problem is solved analytically within the framework of linearized Poisson-Boltzmann theory and classical density functional theory. The governing equation of the electrostatic problem is derived by minimization of the corresponding density functional, which leads to the Debye-Hückel equation. Subsequently, the Debye-Hückel equa…
We perform computational investigations of electrolyte-mediated interactions of charged colloidal particles confined within nanochannels. We investigate the role of discrete ion effects, valence, and electrolyte strength on colloid-wall interactions. We find for some of the multivalent charge regimes that the like-charged colloids and walls can have attractive interactions. We study in detail these interactions and the free energy profile for the colloid-wall separation. We find there are energy barriers and energy minima giving preferred colloid locations in the channel near the center and at…
We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerab…
The renormalized charge of a simple two-dimensional model of colloidal suspension was determined by solving the hypernetted chain approximation and Ornstein-Zernike equations. At the infinite dilution limit, the asymptotic behavior of the correlations functions is used to define the effective interactions between the components of the system and these effective interactions were compared to those derived from the Poisson-Boltzmann theory. The results we obtained show that, in contrast to the mean-field theory, the renormalized charge does not saturate, but exhibits a maximum value and then dec…
In this paper, we theoretically study the electrostatic interaction between a pair of identical colloids with constant surface potentials sitting in close vicinity of each other at a fluid interface. By employing a simplified yet reasonable model system, the problem is solved within the framework of classical density functional theory and linearized as well as nonlinear Poisson-Boltzmann (PB) theory. Apart from providing a sound theoretical framework generally applicable to any such problem, our novel findings, all of which contradict common beliefs, include the following: first, quantitative …
