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Register a new userPhase Behavior of Aqueous Suspension of Laponite: New Insights with Microscopic Evidence
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Investigating microstructure of suspensions with particles having anisotropic shape that share complex interactions is a challenging task leading to competing claims. This work investigates phase behavior of one such system: aqueous Laponite suspension, which is highly contested in the literature, using rheological and microscopic tools. Remarkably, we observe that over a broad range of Laponite (1.4 to 4 weight %) and salt concentrations (0 to 7 mM), the system overwhelmingly demonstrates all the rheological characteristics of the sol-gel transition leading to a percolated network. Analysis of the rheological response leads to fractal dimension that primarily depends on the Laponite concentration. We also obtain the activation energy for gelation, which is observed to decrease with increase in Laponite as well as salt concentration. Significantly, the cryo-TEM images of the post-gel state clearly show presence of a percolated network formed by inter-particle bonds. The present work therefore conclusively establishes the system to be in an attractive gel state resolving a long-standing debate in the literature.
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Synthetic hectorite clay Laponite RD/XLG is composed of disk-shaped nanoparticles that acquire dissimilar charges when suspended in an aqueous media. Owing to their property to spontaneously self-assemble, Laponite is used as a rheology modifier in a variety of commercial water-based products. Particularly, aqueous dispersion of Laponite undergoes liquid - to - solid transition at about 1 volume % concentration. The evolution of the physical properties as dispersion transforms to solid state is reminiscent of physical aging in molecular as well as colloidal glasses. The corresponding soft glassy dynamics of an aqueous Laponite dispersion, including the rheological behavior, has been extensively studied in the literature. In this feature article we take an overview of recent advances in understanding soft glassy dynamics and various efforts taken to understand the peculiar rheological behaviors. Furthermore, the continuously developing microstructure that is responsible for eventual formation of soft solid state that supports its own weight against gravity has also been a topic of intense debate and discussion. Particularly extensive experimental and theoretical studies lead to two types of microstructures for this system: an attractive gel-like or repulsive glass like. We carefully examine and critically analyze the literature and propose a state diagram that suggests aqueous Laponite dispersion to be present in an attractive gel state.
Aqueous dispersion of Laponite, when exposed to carbon dioxide environment leads to in situ inducement of magnesium and lithium ions, which is, however absent when dispersion is exposed to air. Consequently, in the rheological experiments, Laponite dispersion preserved under carbon dioxide shows more spectacular enhancement in the elastic and viscous moduli as a function of time compared to that exposed to air. By measuring concentration of all the ions present in a dispersion as well as change in pH, the evolving inter-particle interactions among the Laponite particles is estimated. DLVO analysis of a limiting case is performed, wherein two particles approach each other in a parallel fashion a situation with maximum repulsive interactions. Interestingly it is observed that DLVO analysis explains the qualitative details of an evolution of elastic and viscous moduli remarkably well thereby successfully relating the macroscopic phenomena to the microscopic interactions.
Colloidal suspensions that are out of thermodynamic equilibrium undergo physical aging wherein their structure evolves to lower the free energy. In aqueous suspension of Laponite, physical aging accompanies increases of elastic and viscous moduli as a function of time. In this work we study temporal evolution of elastic and viscous moduli at different frequencies and observe that freshly prepared aqueous suspension of Laponite demonstrates identical rheological behavior reported for the crosslinking polymeric materials undergoing chemical gelation. Consequently at a certain time tan{delta} is observed to be independent of frequency. However, for samples preserved under rest condition for longer duration before applying the shear melting, the liquid to solid transition subsequent to shear melting shows greater deviation from classical gelation. We also obtain continuous relaxation time spectra from the frequency dependence of viscous modulus. We observe that, with increase in the rest time, continuous relaxation time spectrum shows gradual variation from negative slope, describing dominance of fast relaxation modes to positive slope representing dominance of slow relaxation modes. We propose that the deviation from gelation behavior for the shear melted suspensions originates from inability of shear melting to completely break the percolated structure thereby creating unbroken aggregates. The volume fraction of such unbroken aggregates increases with the rest time. For small rest times presence of fewer number of unbroken aggregates cause deviation from the classical gelation. On the other hand, at high rest times presence of greater fraction of unbroken aggregates subsequent to shear melting demonstrate dynamic arrest leading to inversion of relaxation time spectra.
In this work we study structural recovery of a soft glassy Laponite suspension by monitoring temporal evolution of elastic modulus under isothermal conditions as well as following step temperature jumps. Interestingly, evolution behavior under isothermal conditions indicates the rate, and not the path of structural recovery, to be dependent on temperature. The experiments carried out under temperature jump conditions however trace a different path of structural recovery, which shows strong dependence on temperature and the direction of change. Further investigation of the system suggests that this behavior can be attributed to restricted mobility of counterions associated with Laponite particle at the time of temperature change, which do not allow counterion concentration to reach equilibrium value associated with the changed temperature. Interestingly this effect is observed to be comparable with other glassy molecular and soft materials, which while evolve in a self-similar fashion under isothermal conditions, show asymmetric behavior upon temperature change.
Aqueous suspensions of Laponite with discotic particles are well-studied and find a wide range of applications in industry. A new direction of their implementation is polymer composites that can exhibit improved physical properties.We have studied the aging of aqueous suspensions of Laponite and sodium polystyrene sulfonate (PSS-Na) and both their microscopic (small-angle X-ray scattering, SAXS) and macroscopic (small amplitude oscillatory shear (SAOS) rheometry) properties. The concentration of Laponite, $C_L$, was fixed at 2.5% wt and concentration of PSS-Na, $C_p$, was varied within 0-0.5% wt (0-24.2~mM). It is shown that the adding of PSS-Na significantly accelerates the aging.Nevertheless, the systems were stable against the sedimentation, and the flocculation didnt occur. Polyelectrolyte induced the appearance of large-scale fractal heterogeneities, which became more compact in the course of the aging. Polyelectrolyte induced the appearance of large-scale fractal heterogeneities, which became more compact in the course of the aging.
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