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Register a new userAging of aqueous laponite dispersions in the presence of sodium polystyrene sulfonate
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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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This work discusses the sedimentation stability and aging of aqueous suspension of Laponite in the presence of cetyltrimethylammonium bromide (CTAB). The concentration of Laponite was fixed at the constant level $C_l=2$ %wt, which corresponds to the threshold between equilibrium gel IG$_1$ and repulsive gel IG$_2$ phases. The concentration of CTAB $C_s$ was within 0-0.3 %wt. In the presence of CTAB the Laponite aqueous suspensions were unstable against sedimentation and they separated out into upper and bottom layers (U- and B-layers, respectively). The dynamic light scattering technique revealed that the addition of CTAB even at rather small concentration, $C_s=0.0164$ %wt ($0.03 CEC$), induced noticeable changes in the aging dynamics of U-layer, and it was explained by equilibration of CTAB molecules that were initially non-uniformly distributed between different Laponite particles. Accelerated stability analysis by means of analytical centrifugation with rotor speed ${omega}=500-4000$ rpm revealed three sedimentation regimes: continuous (I, $C_s<0.14$ %wt), zone-like (II, $0.14<C_s<0.2$ %wt) and gel-like (III, $C_s >0.2$ %wt). It was demonstrated that B-layer was soft in the zone-like regime. The increase of ${omega}$ resulted in its supplementary compressing and the collapse of soft sediment above certain critical centrifugal acceleration.
The aging behavior is investigated for thin films of atactic polystyrene through measurements of complex electric capacitance. During isothermal aging process the real part of the electric capacitance increases with aging time, while the imaginary part decreases with aging time. This result suggests that the aging time dependence of the real and imaginary parts are mainly associated with change in thickness and dielectric permittivity, respectively. In thin films, the thickness depends on thermal history of aging even above the glass transition. Memory and `rejuvenation effects are also observed in the thin films.
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.
We investigate physical origin of ergodicity breaking in an aqueous colloidal dispersion of synthetic hectorite clay, LAPONITE(R), by performing dissolution and rheological experiments with monovalent salt and tetrasodium pyrophosphate solution. We also study the effect of interface, nitrogen and paraffin oil on the same. Dissolution experiments carried out for dispersions with both the interfaces show similar results. However, for samples with nitrogen interface, all the effects are observed to get expedited in time compared to paraffin oil interface. When kept in contact with water, 1.5 wt. % and 2.8 wt. % colloidal dispersion at pH 10 swell at small ages, while do not swell at large ages. The solution of tetrasodium pyrophosphate, interestingly, dissolves the entire colloidal dispersion samples with pH 10 irrespective of the clay concentration. Experiments carried out on colloidal dispersions prepared in water having pH 13 demonstrate no effect of water as well as sodium pyrophosphate solution on the same suggesting a possibility of the presence of negative charge on edge at that pH. We believe that all the behaviors observed for samples at pH 10 can be explained by an attractive gel microstructure formed by edge-to-face contact. Furthermore, the absence of swelling in old colloidal dispersion at pH 10 and dissolution of the same by sodium pyrophosphate solution cannot be explained by merely repulsive interactions. This behavior suggests that attractive interactions play an important role in causing ergodicity breaking in the colloidal dispersions at pH 10 at all the ages irrespective of the clay concentration. We substantiate the presence of fractal network structure formed by interparticle edge-face association using rheological tools and cryo-TEM imaging. We also conduct a comprehensive study of the effect of sodium pyrophosphate in the sol-gel transition of LAPONITE(R) dispersion.
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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