Na-montmorillonite is a natural clay mineral and is available in abundance in nature. The aqueous dispersions of charged and anisotropic platelets of this mineral exhibit non-ergodic kinetically arrested states ranging from soft glassy phases dominat
ed by interparticle repulsions to colloidal gels stabilized by salt induced attractive interactions. When the salt concentration in the dispersing medium is varied systematically, viscoelasticity and yield stress of the dispersion show non-monotonic behavior at a critical salt concentration, thus signifying a morphological change in the dispersion microstructures. We directly visualize the microscopic structures of these kinetically arrested phases using cryogenic scanning electron microscopy. We observe the existence of honeycomb-like network morphologies for a wide range of salt concentrations. The transition of the gel morphology, dominated by overlapping coin (OC) and house of cards (HoC) associations of clay particles at low salt concentrations to a new network structure dominated by face-face coagulation of platelets, is observed across the critical salt concentration. We further assess the stability of these gels under gravity using electroacoustics. This study, performed for concentrated clay dispersions for a wide concentration range of externally added salt, is useful in our understanding of many geophysical phenomena that involve the salt induced aggregation of natural clay minerals.
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 $D$, which signifies the deviation from Arrhenius behavior, is obtained from fits to the time evolutions of the structural relaxation timescales. For the Laponite suspensions studied in this work, $D$ is seen to be independent of $C_{L}$ and $C_{S}$, but is weakly dependent on $T$. Interestingly, the behavior of $D$ corroborates the behavior of fragility in molecular glass formers with respect to equivalent variables. Furthermore, the stretching exponent $beta$, which quantifies the width $w$ of the spectrum of structural relaxation timescales is seen to depend on $t_{w}$. A hypothetical Kauzmann time $t_{k}$, analogous to the Kauzmann temperature for molecular glasses, is defined as the timescale at which $w$ diverges. Corresponding to the Vogel temperature defined for molecular glasses, a hypothetical Vogel time $t^{infty}_{alpha}$ is also defined as the time at which the structural relaxation time diverges. Interestingly, a correlation is observed between $t_{k}$ and $t^{infty}_{alpha}$, which is remarkably similar to that known for fragile molecular glass formers. A coupling model that accounts for the $t_{w}$-dependence of the stretching exponent is used to analyse and explain the observed correlation between $t_{k}$ and $t^{infty}_{alpha}$.
When calcium salts are added to an aqueous solution of polysaccharide pectin, ionic cross-links form between pectin chains, giving rise to a gel network in dilute solution. In this work, dynamic light scattering (DLS) is employed to study the microsc
opic dynamics of the fractal aggregates (flocs) that constitute the gels, while rheological measurements are performed to study the process of gel rupture. As calcium salt concentration is increased, DLS experiments reveal that the polydispersities of the flocs increase simultaneously with the characteristic relaxation times of the gel network. Above a critical salt concentration, the flocs become interlinked to form a reaction-limited fractal gel network. Rheological studies demonstrate that the limits of the linear rheological response and the critical stresses required to rupture these networks both decrease with increase in salt concentration. These features indicate that the ion-mediated pectin gels studied here lie in a `strong link regime that is characterised by inter-floc links that are stronger than intra-floc links. A scaling analysis of the experimental data presented here demonstrates that the elasticities of the individual fractal flocs exhibit power-law dependences on the added salt concentration. We conclude that when pectin and salt concentrations are both increased, the number of fractal flocs of pectin increases simultaneously with the density of crosslinks, giving rise to very large values of the bulk elastic modulus.
The dispersion processes of aqueous samples of clay are studied using ultrasound attenuation spectroscopy. The attenuation spectra that are acquired in the frequency range $10-100$ MHz are used to determine the particle size distributions (PSDs) for
different concentrations and ages of the clay suspensions. Our analysis, using equivalent spherical diameter (ESD) for circular discs under Stokes drag in samples of concentrations greater than 1.5% w/v, shows that a substantial fraction of the aggregates in suspension are actually tactoids that are composed of more than one platelet. This is in contrast to the general belief that clay disperses into individual platelets in the concentration range where their suspensions exhibit glassy behavior. We conclude that the incomplete fragmentation of the clay tactoids arises from the rapid enhancement of the inter-tactoid Coulombic repulsion.
Three drugs, Ibuprofen, Aspirin and Erythromycin, are encapsulated in spherical Pluronic F127 micelles. The shapes and the size distributions of the micelles in dilute, aqueous solutions, with and without drugs, are ascertained using cryo- Scanning E
lectron Microscopy and Dynamic Light Scattering (DLS) experiments, respectively. Uptake of drugs above a threshold concentration is seen to reduce the critical micellization temperature of the solution. The mean hydrodynamic radii and polydispersities of the micelles are found to increase with decrease in temperature and in the presence of drug molecules. The hydration of the micellar core at lower temperatures is verified using fluorescence measurements. Increasing solution pH leads to the ionization of the drugs incorporated in the micellar cores. This causes rupture of the micelles and release of the drugs into the solution at the highest solution pH value of 11.36 investigated here and is studied using DLS and fluorescence spectrocopy.
The primary and secondary relaxation timescales of aging colloidal suspensions of Laponite are estimated from intensity autocorrelation functions obtained in dynamic light scattering (DLS) experiments. The dynamical slowing down of these relaxation p
rocesses are compared with observations in fragile supercooled liquids by establishing a one-to-one mapping between the waiting time since filtration of a Laponite suspension and the inverse of the temperature of a supercooled liquid that is rapidly quenched towards its glass transition temperature. New timescales, such as the Vogel time and the Kauzmann time, are extracted to describe the phenomenon of dynamical arrest in Laponite suspensions. In results that are strongly reminiscent of those extracted from supercooled liquids approaching their glass transitions, it is demonstrated that the Vogel time calculated for each Laponite concentration is approximately equal to the Kauzmann time, and that a strong coupling exists between the primary and secondary relaxation processes of aging Laponite suspensions. Furthermore, the experimental data presented here clearly demonstrates the self-similar nature of the aging dynamics of Laponite suspensions within a range of sample concentrations.
Soft materials such as colloidal suspensions, polymer solutions and liquid crystals are constituted by mesoscopic entities held together by weak forces. Their mechanical moduli are several orders of magnitude lower than those of atomic solids. The ap
plication of small to moderate stresses to these materials results in the disruption of their microstructures. The resulting flow is non-Newtonian and is characterised by features such as shear rate-dependent viscosities and non-zero normal stresses. This article begins with an introduction to some unusual flow properties displayed by soft matter. Experiments that report a spectrum of novel phenomena exhibited by these materials, such as turbulent drag reduction, elastic turbulence, the formation of shear bands and the existence of rheological chaos, flow-induced birefringence and the unusual rheology of soft glassy materials, are reviewed. The focus then shifts to observations of the liquid-like response of granular media that have been subjected to external forces. The article concludes with examples of the patterns that emerge when certain soft materials are vibrated, or when they are displaced with Newtonian fluids of lower viscosities.
The Brazil-nut effect is the phenomenon in which a large intruder particle immersed in a vertically shaken bed of smaller particles rises to the top, even when it is much denser. The usual practice, while describing these experiments, has been to use
the dimensionless acceleration Gamma=a omega^2/g, where a and omega are respectively the amplitude and the angular frequency of vibration and g is the acceleration due to gravity. Considering a vibrated quasi-two-dimensional bed of mustard seeds, we show here that the peak-to-peak velocity of shaking v= aomega, rather than Gamma, is the relevant parameter in the regime where boundary-driven granular convection is the main driving mechanism. We find that the rise-time tau of an intruder is described by the scaling law tau ~ (v-v_c)^{-alpha}, where v_c is identified as the critical vibration velocity for the onset of convective motion of the mustard seeds. This scaling form holds over a wide range of (a,omega), diameter and density of the intruder.
Photon correlation spectroscopy and rheological measurements are performed to investigate the microscopic dynamics and mechanical responses of aqueous solutions of triblock copolymers and aqueous mixtures of triblock copolymers and anionic surfactant
s. Increasing the concentration of triblock copolymers results in a sharp increase in the magnitude of the complex moduli characterising the samples. This is understood in terms of the changes in the aggregation and packing behaviours of the copolymers and the constraints imposed upon their dynamics due to increased close packing. The addition of suitable quantities of an anionic surfactant to a strongly elastic copolymer solution results in a decrease in the complex moduli of the samples by several decades. It is argued that the shape anisotropy and size polydispersity of the micelles comprising mixtures cause dramatic changes in the packing behaviour, resulting in sample unjamming and the observed decrease in complex moduli. Finally, a phase diagram is constructed in the temperature-surfactant concentration plane to summarise the jamming-unjamming behaviour of aggregates constituting triblock copolymer-anionic surfactant mixtures.
We investigate the stress relaxation behavior on the application of step strains to aging aqueous suspensions of the synthetic clay Laponite. The stress exhibits a two-step decay, from which the slow relaxation modes are extracted as functions of the
sample ages and applied step strain deformations. Interestingly, the slow time scales that we estimate show a dramatic enhancement with increasing strain amplitudes. We argue that the system ends up exploring the deeper sections of its energy landscape following the application of the step strain.
