Yogesh M. Joshi

Rheological behaviour of aqueous suspensions of laponite: new insights into the ageing phenomena

In this paper, the ageing behaviour of suspensions of laponite with varying salt concentration is investigated using rheological tools. It is observed that ageing is accompanied by an increase in the complex viscosity. The creep experiments performed at various ages show damped oscillations in the strain. The characteristic time scale of the damped oscillations, the retardation time, shows a prominent decrease with increasing age of the system. However, this dependence weakens with an increase in the salt concentration, which is known to change the microstructure of the system from glass like to gel like. We postulate that a decrease in the retardation time can be represented as a decrease in the viscosity (friction) of the dissipative environment surrounding the arrested entities that oppose elastic deformation of the system. We believe that ageing in colloidal glass leads to a greater ordering that enhances relative spacing between the constituents, thereby reducing the frictional resistance. However, since a gel state is inherently different in structure (fractal network) to that of a glass state (disordered), ageing in the gel does not induce ordering. Consequently, we observe an inverse dependence of retardation time on age, which becomes weaker with an increase in the salt concentration. We analyse these results from the perspective of ageing dynamics of both glass and gel states of laponite suspensions.

Irreversible aging dynamics and generic phase behavior of aqueous suspensions of Laponite.

We study the aging behavior of aqueous suspension of Laponite having 2.8 wt % concentration using rheological tools. At various salt concentration all the samples demonstrate orientational order when observed using crossed polarizers. In rheological experiments we observe inherent irreversibility in the aging dynamics which forces the system not to rejuvenate to the same state in the shear melting experiment carried out at a later date since preparation. The extensive rheological experiments carried out as a function of time elapsed since preparation demonstrate the self-similar trend in the aging behavior irrespective of the concentration of salt. We observe that the exploration of the low-energy states as a function of aging time is only kinetically affected by the presence of salt. We estimate that the energy barrier to attain the low-energy states decreases linearly with increase in the concentration of salt. The observed superposition of all the elapsed time and the salt-concentration-dependent data suggests that the aging that occurs in low salt concentration systems over a very long period is qualitatively similar to the aging behavior observed in systems with high salt concentration over a shorter period.

Physicochemical effects in aging aqueous Laponite suspensions.

We study aging behavior of an aqueous suspension of Laponite as a function of concentration of Laponite, concentration of salt, time elapsed since preparation of suspension (idle time), and temperature by carrying extensive rheological and conductivity experiments. We observe that temporal evolution of elastic moduli, which describes structural build-up and aging, shifts to low times for experiments carried out for higher concentration of Laponite, higher concentration of salt, greater temperature, and longer idle time while preserving the curvature of evolution in the solid regime (elastic modulus greater than viscous modulus). Consequently appropriate shifting of evolution of elastic modulus in the solid regime leads to aging time-idle time-salt concentration-Laponite concentration-temperature superposition. The existence of such a superposition suggests the generic nature of microstructure buildup irrespective of mentioned variables in the explored range. The behavior of shift factors needed to obtain the superposition indicate that the energy barrier associated with structural buildup decreases with an increase in idle time and temperature and decreases linearly with an increase in concentration of Laponite and that of salt. The conductivity experiments show that ionic conductivity of the suspension increases with increasing Laponite concentration, salt concentration, temperature, and very importantly the idle time. We also analyze the interparticle interactions using DLVO theory that suggests an increase in idle time, temperature, and salt concentration increases the height of the repulsive energy barrier while it decreases the width of the same when particles approach each other in a parallel fashion. However when particles approach each other in a perpendicular fashion, owing to dissimilar charges on edge and face, the energy barrier for the attractive interaction is expected to decrease with an increase in idle time, temperature, and salt concentration. Analysis of rheological and conductivity experiments suggests a strong influence of attractive interactions on the low energy structures in an aqueous suspension of Laponite.

Rupture of entangled polymeric liquids in elongational flow

Polymer melts and concentrated solutions rupture at high rates of elongation in a manner that is reminiscent of the cohesive failure of solids. We propose a simple molecular picture of rupture of a polymer filament, in which catastrophic failure occurs when the frictional force on an entangled chain can no longer balance the tension in the chain. The model, which is fully predictive and contains no adjustable parameters, captures the rupture characteristics of the available data sets and agrees quantitatively with critical stress–critical strain data and the dependence of critical strain on the Weissenberg number.

Model for cage formation in colloidal suspension of laponite

In this paper we investigate glass transition in aqueous suspension of synthetic hectorite clay, laponite. We believe that upon dispersing laponite clay in water, the system comprises of clusters (agglomerates) of laponite dispersed in the same. Subsequent osmotic swelling of these clusters leads to an increase in their volume fraction. We propose that this phenomenon is responsible for slowing down of the overall dynamics of the system. As clusters fill up the space, the system undergoes glass transition. Along with the mode coupling theory, the proposed mechanism rightly captures various characteristic features of the system in the ergodic regime as it approaches glass transition.

Slipping fluids: a unified transient network model

Wall slip in polymer solutions and melts play an important role in fluid flow, heat transfer and mass transfer near solid boundaries. Several different physical mechanisms have been suggested for wall slip in entangled systems. We look at the wall slip phenomenon from the point of view of a transient network model, which is suitable for describing both, entangled solutions and melts. We propose a model, which brings about unification of different mechanisms for slip. We assume that the surface is of very high energy and the dynamics of chain entanglement and disentanglement at the wall is different from those in the bulk. We show that severe disentanglement in the annular wall region of one radius of gyration thickness can give rise to non-monotonic flow curve locally in that region. By proposing suitable functions for the chain dynamics so as to capture the right physics, we show that the model can predict all features of wall slip, such as flow enhancement, diameter-dependent flow curves, discontinuous increase in flow rate at a critical stress, hysteresis in flow curves, the possibility of pressure oscillations in extrusion and a second critical wall shear stress at which another jump in flow rate can occur.

Prediction of long and short time rheological behavior in soft glassy materials.

We present an effective time approach to predict long and short time rheological behavior of soft glassy materials from experiments carried out over practical time scales. Effective time approach takes advantage of relaxation time dependence on aging time that allows time-aging time superposition even when aging occurs over the experimental time scales. Interestingly, experiments on a variety of soft materials demonstrate that the effective time approach successfully predicts superposition for diverse aging regimes ranging from subaging to hyperaging behaviors. This approach can also be used to predict behavior of any response function in molecular as well as spin glasses.

Dynamics of Colloidal Glasses and Gels

Many household and industrially important soft colloidal materials, such as pastes, concentrated suspensions and emulsions, foams, slurries, inks, and paints, are very viscous and do not flow over practical timescales until sufficient stress is applied. This behavior originates from restricted mobility of the constituents arrested in disordered structures of varying length scales, termed colloidal glasses and gels. Usually these materials are thermodynamically out of equilibrium, which induces a time-dependent evolution of the structure and the properties. This review presents an overview of the rheological behavior of this class of materials. We discuss the experimental observations and theoretical developments regarding the microstructure of these materials, emphasizing the complex coupling between the deformation field and nonequilibrium structures in colloidal glasses and gels, which leads to a rich array of rheological behaviors with profound implications for various industrial processes and products.

Effect of temperature on aging and time–temperature superposition in nonergodic laponite suspensions

We have studied the effect of temperature on the aging dynamics of laponite suspensions by carrying out the rheological oscillatory and creep experiments. We observed that at higher temperatures the mechanism responsible for aging became faster thereby shifting the evolution of elastic modulus to lower ages. Significantly, in the creep experiments, all the aging time and the temperature dependent strain data superposed to form a master curve. The possibility of such a superposition suggests that the rheological behavior depends on the temperature and the aging time only through the relaxation processes and both the variables do not affect the distribution but only the average value of the relaxation times. In addition, this procedure allows us to predict long time rheological behavior by carrying out short time tests at high temperatures and small ages.

A unified wall slip model

A unified slip model is developed, which predicts wall slip by either a disentanglement mechanism or by debonding mechanism, depending upon the adhesive energy of the wall-polymer pair. The model is based on the transient network theory, in which the activation processes of adsorption and desorption are considered to occur at the wall in parallel to the stretching of the adsorbed chains. It is shown that the stick-slip transition occurs due to the local non-monotonic flow behavior near the wall irrespective of the mechanism of slip. The model predictions of the critical wall shear stress are in good agreement with experimentally observed values of the critical stress for various adhesive energies of wall polymer pair. Another important prediction of the model is that the temperature dependence of the critical wall shear stress for debonding is different than that of disentanglement mechanism under certain experimental conditions. This may be useful for discerning the correct mechanism of slip. The unified model encompasses different systems (viz. entangled solutions and melts) and diverse mechanisms (viz. disentanglement and debonding) in a common mathematical framework.