Aqueous Suspension Of Laponite Research Articles

Quantifying the destructuring of a thixotropic colloidal suspension using falling ball viscometry

The settling dynamics of falling spheres inside a Laponite suspension is studied. Laponite is a colloidal synthetic clay that shows physical aging in aqueous suspensions due to the spontaneous evolution of inter-particle electrostatic interactions. In our experiments, millimeter-sized steel balls are dropped in aqueous Laponite suspensions of different ages (i.e., time elapsed since sample preparation). The motion of the falling balls is captured using a high-speed camera, and the velocities of their centroids are estimated from the images. Interestingly, we observe that balls of larger diameters fail to achieve terminal velocity over the entire duration of the experiment. We propose a mathematical model that accounts for rapid structural changes (expected to be induced by the falling ball) in Laponite suspensions whose aging time scales are much slower than the time of fall of the ball. For a range of ball sizes and Laponite suspension ages, our model correctly predicts the time dependence of the ball velocity. Furthermore, fits to our model allow us to estimate the rates of destructuring of the thixotropic suspensions due to the passage of the falling ball.

Microscopic ergodicity breaking governs the emergence and evolution of elasticity in glass-forming nanoclay suspensions.

We report a study combining x-ray photon correlation spectroscopy (XPCS) with in situ rheology to investigate the microscopic dynamics and mechanical properties of aqueous suspensions of the synthetic hectorite clay Laponite, which is composed of charged, nanometer-scale, disk-shaped particles. The suspensions, with particle concentrations ranging from 3.25 to 3.75 wt%, evolve over time from a fluid to a soft glass that displays aging behavior. The XPCS measurements characterize the localization of the particles during the formation and aging of the soft-glass state. The fraction of localized particles, f_{0}, increases rapidly during the early formation stage and grows more slowly during subsequent aging, while the characteristic localization length r_{loc} steadily decreases. Despite the strongly varying rates of aging at different concentrations, both f_{0} and r_{loc} scale with the elastic shear modulus G^{'} in a manner independent of concentration. During the later aging stage, the scaling between r_{loc} and G^{'} agrees quantitatively with a prediction of naive mode coupling theory. Breakdown of agreement with the theory during the early formation stage indicates the prevalence of dynamic heterogeneity, suggesting the soft solid forms through precursors of dynamically localized clusters.

Boltzmann superposition principle for a time-dependent soft material: assessment under creep flow field

Variety of time-dependent soft materials that undergo evolution of microstructure are known to follow the Boltzmann superposition principle when appropriately transformed from the real to the effective time domain. This behavior is attributed to obliteration of time dependency in the effective time domain by normalizing the real time by the time-dependent relaxation time. This work is aimed at assessing validity of the Boltzmann superposition principle in the effective time domain under application of step changes and ramps in stress for a time-dependent soft glassy material: an aqueous suspension of Laponite, whose rheological properties are known to show strong time and stress dependency. Interestingly, creep experiments started at different aging times and for different constant stresses indeed lead to a comprehensive time–aging time–stress superposition resulting in time and stress dependence of relaxation time and modulus. Subsequently, we analyze compliance response of the material to different kinds of stress step change and ramp combinations. We observe that except few, most of the compliance data plotted in the effective time domain does not overlap on the comprehensive superposition. We analyze this behavior and attribute the observed mismatch to the history dependence of the time evolution of modulus.

Phase Behavior of Aqueous Suspension of Laponite: New Insights with Microscopic Evidence.

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 wt %) 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 postgel state clearly show the presence of a percolated network formed by interparticle bonds. The present work therefore conclusively establishes the system to be in an attractive gel state resolving a long-standing debate in the literature.

Polymer concentration regulated aging in aqueous Laponite suspensions

By rheologically examining poly(vinyl alcohol)-water-Laponite multicomponent suspensions, we report evidence of concentration of adsorbing polymer strictly regulating the aging dynamics in multicomponent Laponite suspensions. The study is performed in the dilute polymer concentration regime. We analyze the observed aging pattern by fixing the non-monotonic transitions observed between temporally achieved suspension elastic moduli and polymer concentration, as the border of a sub-regime. This divides the aging pattern into three sub-regimes, across which the suspension elastic modulus shows an oscillatory relationship with polymer concentration. We also observe that suspensions belonging to first two sub-regimes remained colloidally stable during the timescale of measurement. In the third sub-regime, macrophase separation occurred, while suspensions were aging. For an explanation to this observation, we conducted three complementary measurements on select suspensions from each sub-regime, after they attained structurally arrested state. They are (a) small-angle neutron scattering, (b) structure recovery upon shear melting, and (c) zeta potential estimation. The collective evidences are analyzed to reach a possible explanation. The observation and analysis highlight the effect of concentration of adsorbing polymer on aging clay suspensions and have direct applications in stabilization, rheology modification, as well as polymer nanocomposite preparation.

Passive microrheology in the effective time domain: analyzing time dependent colloidal dispersions.

We studied the aging dynamics of an aqueous suspension of LAPONITE®, a model time dependent soft glassy material, using a passive microrheology technique. This system is known to undergo physical aging during which its microstructure evolves progressively to explore lower free energy states. Optical microscopy is used to monitor the motion of micron-sized tracer probes embedded in a sample kept between two glass plates. The mean square displacements (MSD) obtained from the motion of the tracer particles show a systematic change from a purely diffusive behavior at short aging times to a subdiffusive behavior as the material ages. Interestingly, the MSDs at all the aging times as well as different LAPONITE® concentrations superpose remarkably to show a time-aging time master curve when the system is transformed from the real time domain to the effective time domain, which is obtained by rescaling the material clock to account for the age dependent relaxation time. The transformation of the master curve from the effective time domain to the real time domain leads to the prediction of the MSD in real time over a span of 5 decades when the measured data at individual aging times are only over 2 decades. Since the MSD obtained from microrheology is proportional to the creep compliance of a material, by using the Boltzmann superposition principle along with the convolution relation in the effective time domain, we predict the stress relaxation behavior of the system in real time. This work shows that the effective time approach applied to microrheology facilitates the prediction of long time creep and relaxation dynamics of a time dependent soft material by carrying out short time experiments at different aging times.

Neutron diffraction study of aqueous Laponite suspensions at the NIMROD diffractometer.

The process of dynamical arrest, leading to formation of different arrested states such as glasses and gels, along with the closely related process of aging, is central for both basic research and technology. Here we report on a study of the time-dependent structural evolution of two aqueous Laponite clay suspensions at different weight concentrations. Neutron diffraction experiments have been performed with the near and intermediate range order diffractometer (NIMROD) that allows studies of the structure of liquids and disordered materials over a continuous length scale ranging from 1 to 300 Å, i.e., from the atomistic to the mesoscopic scales. NIMROD is presently a unique diffractometer, bridging the length scales traditionally investigated by small angle neutron scattering or small angle x-ray scattering with that accessible by traditional diffractometers for liquids. Interestingly, we have unveiled a signature of aging of both suspensions in the length scale region of NIMROD. This phenomenon, ascribed to sporadic contacts between Laponite platelets at long times, has been observed with the sample arrested as gel or as repulsive glass. Moreover, water molecules within the layers closest to Laponite platelets surface show orientational and translational order, which maps into the crystalline structure of Laponite.

Rheological signatures of gelation and effect of shear melting on aging colloidal suspension

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.

Hybrid multiwalled carbon nanotube − Laponite sorbent for removal of methylene blue from aqueous solutions

The article discusses adsorption of methylene blue dye by novel hybrid sorbent consisting of Laponite and multiwalled carbon nanotubes. The sorbent was obtained by sonication of the aqueous suspensions of nanotubes at different concentrations of Laponite. The methods of the methylene blue adsorption, dead-end membrane filtration and environmental scanning electron microscopy were used for the sorbent characterization.It may be concluded from the results of filtration and adsorption experiments that sonication of mixed aqueous suspensions of Laponite and multiwalled carbon nanotubes leads to the formation of hybrid particles (ML-particles) with a core–shell structure. The size and the shape of hybrid particles were determined by nanotubes, while their adsorption properties were determined by Laponite particles attached to the surface of nanotubes. The Laponite content in hybrid particles was corresponding to the Laponite to nanotubes ratio in the initial suspension XL=0–1.Due to the presence of Laponite in the sorbent, its adsorbing capacity was much higher as compared to the adsorbing capacity of pure nanotubes, and it was directly proportional to the Laponite content. This sorbent may be used either as a purifying additive or as a filtering layer if it is deposited on the surface of a supporting membrane. Due to relatively large size of hybrid particles, they can be easily separated from the purified solution by filtration or centrifugation.

Старіння водних суспензій лапоніту в присутності полістирол сульфонату натрію

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, CL, was fixed at 2.5% wt and concentration of PSS–Na, Cp, 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 didn’t occur. Polyelectrolyte induced the appearance of large-scale fractal heterogeneities, which became more compact in the course of the aging.

Sedimentation stability and aging of aqueous dispersions of Laponite in the presence of cetyltrimethylammonium bromide

This work discusses the sedimentation stability and aging of aqueous suspensions of Laponite in the presence of cetyltrimethylammonium bromide (CTAB). The concentration of Laponite was fixed at a constant level C(l)=2%wt, which corresponds to the threshold between equilibrium gel IG(1) and glass IG(2) states. 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 separated into the upper and bottom layers (U and B layers, respectively). The dynamic light-scattering technique has revealed that addition of CTAB even at a rather small concentration, C(s)=0.0164 %wt (0.03 cation exchange capacity), induced noticeable changes in the aging dynamics of the U layer. It was explained by equilibration of CTAB molecules that were initially nonuniformly distributed between different Laponite particles. Accelerated stability analysis by means of analytical centrifugation with rotor speed ω=500-4000 rpm revealed three sedimentation regimes: continuous (I, C(s)<0.14 %wt), zonelike (II, 0.14<C(s)<0.2%wt), and gel-like (III, C(s)>0.2%wt). It was demonstrated that the B layer was "soft" in the zonelike regime. The increase of ω resulted in its supplementary compressing and collapse of "soft" sediment above certain critical centrifugal acceleration. The physical nature of the observed behavior, accounting for enhancement of hydrophobic interactions between Laponite particles, is discussed.

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.

Mechanical behavior and stimuli-response of nanocomposite hydrogels

Nanocomposite hydrogels (NC gels) have been intensively studied up to now among all the high performance hydrogels due to the facile preparation, unique composition, and excellent properties of mechanical, optical, and swelling/deswelling. We have achieved some significant results in the mechanical behavior of the NC gels and the synthesis of stimuli-response NC gels during several years. Ultrahigh extensibility was found from the as-prepared and swelling-equilibrated poly(N-isopropylacrylamide) (PNIPAm)-hectorite Laponite NC gels with strain hardening at large strain region. Mooney-Rivlin function was found available to describe the stress-strain behavior under compression, but failed to predict the high strain hardening. Creton model was adopted to interpret the stress-strain curves for the NC gels under large deformation well, especially the strain hardening in these gels. For the NC gels, the effective cross-linking density was estimated from the equilibrium shear modulus under small strain, the hysteresis was observed during a deformation-recovery cycle, and the relaxation exponent was determined based on the relaxation modulus. According to these results, we suggest that the ultrahigh extensibility of the NC gels is originated from low cross-linking density and moderate relaxation. In respect of stimuli-response NC gel preparation, a stability window was found from aqueous Laponite suspensions for NIPAm copolymerization with ionic monomers to avoid flocculation and precipitation of Laponite platelets. In this way, the pH response and pH/temperature dual response homogeneous NC gels with ultrahigh extensibility were successfully synthesized. Finally, the unsolved scientific problems concerning the NC gels and the potential applications in the near future were discussed.

Hyper-Aging Dynamics of Nanoclay Suspension

Aqueous suspension of nanoclay Laponite undergoes structural evolution as a function of time, which enhances its elasticity and relaxation time. In this work, we employ an effective time approach to investigate long-term relaxation dynamics by carrying out creep experiments. Typically, we observe that the monotonic evolution of elastic modulus shifts to lower aging times, while maxima in viscous moduli get progressively broader for experiments carried out on a later date after preparation (idle time) of the nanoclay suspension. Application of effective time theory produces a superposition of all the creep curves irrespective of their initial state. The resulting dependence of the relaxation time on aging time shows very strong hyper-aging dynamics at short idle times, which progressively weakens to demonstrate a linear dependence in the limit of very long idle times. Remarkably, this behavior of nanoclay suspensions is akin to that observed for polymeric glasses. Consideration of aging as a first-order process suggests that continued hyper-aging dynamics causes cessation of aging. The dependence of relaxation time on aging time, therefore, must attenuate eventually producing linear or weaker dependence on time in order to approach a progressively low-energy state in the limit of very long times as observed experimentally. We also develop a simple scaling model based on a concept of aging of an energy well, which qualitatively captures various experimental observations very well, leading to profound insight into the hyper-aging dynamics of nanoclay suspensions.

Effect of adsorbed poly(ethylene glycol) on the gelation evolution of Laponite suspensions: Aging time-polymer concentration superposition

The effects of the concentration of polyethylene glycol (PEG) and NaCl on the gelation kinetics of aqueous Laponite suspensions were investigated. The PEG concentration cp was increased from 0.063wt.% to 1.0wt.%, and the NaCl concentration cs was increased from 3.0mM to 5.0mM. The gelation process was monitored with the small amplitude oscillatory shear (SAOS) rheology. At each NaCl concentration, the time curves of storage and loss moduli G′ and G″ at different PEG concentrations were shifted horizontally to construct a master curve. Master curves for different NaCl concentrations were shifted further into a main master curve. The results were understood in terms of an increase in steric repulsion with increasing cp. A model based on the theory of interaction-limited coagulation was proposed to describe the dependence of the shift factor on the PEG concentration, taking into account of the interactions between particles. The quantitative description of the observed results has been achieved with this model.

Isotopic effect on the aging dynamics of a charged colloidal system

A dynamic light scattering (DLS) investigation of the isotopic H/D substitution on water molecules in aqueous Laponite suspensions is reported for two Laponite weight concentrations (Cw = 1.5% and Cw = 3.0%). Increasing the deuterium percentage results in a slowing down of the dynamics for both concentrations, although the aging behavior of the suspensions is not qualitatively modified by the isotopic substitution. A scaling law for the isotopic effect is found. The relaxation times and the stretching parameters collapse on two distinct master curves, indicating that the two previously found dynamical behaviors of colloidal gels and glasses are preserved. These results may facilitate a large variety of experimental techniques and further theoretical investigations about the role of the solvent in determining the interaction potential.

Delayed yielding in creep, time–stress superposition and effective time theory for a soft glass

In this work we investigate creep flow of aqueous suspension of Laponite, a model soft glassy material, at different aging times and stresses. We observe that this system shows time - aging time - stress superposition over a range of aging times and stresses when real time scale is transformed into effective time scale. Existence of superposition in an effective time domain facilitates prediction of long and very short time rheological behavior. Analysis of the observed behavior from effective time approach suggests that superposition is possible only when the shape of a relaxation time spectrum is preserved at various aging times and stresses. We also observe that creep curves at low aging times and greater stresses demonstrate delayed but sudden yielding. The critical time, at which material yields, increases with increase in aging time and decrease in stress. We argue that local rejuvenation of part of the glassy material causes variation in the rate of evolution of relaxation modes. The resulting interplay between aging and rejuvenating modes lead to delayed yielding as observed experimentally.

Delayed solidification of soft glasses: new experiments, and a theoretical challenge

When subjected to large amplitude oscillatory shear stress, aqueous Laponite suspensions show an abrupt solidification transition after a long delay time t(c). We measure the dependence of t(c) on stress amplitude, frequency, and on the age-dependent initial loss modulus. At first sight our observations appear quantitatively consistent with a simple soft-glassy rheology (SGR)-type model, in which barrier crossings by mesoscopic elements are purely strain-induced. For a given strain amplitude gamma0 each element can be classified as fluid or solid according to whether its local yield strain exceeds gamma0. Each cycle, the barrier heights E of yielded elements are reassigned according to a fixed prior distribution rho(E): this fixes the per-cycle probability R(gamma0) of a fluid elements becoming solid. As the fraction of solid elements builds up, gamma0 falls (at constant stress amplitude), so R(gamma0) increases. This positive feedback accounts for the sudden solidification after a long delay. The model thus appears to directly link macroscopic rheology with mesoscopic barrier height statistics: within its precepts, our data point towards a power law for rho(E) rather than the exponential form usually assumed in SGR. However, despite this apparent success, closer investigation shows that the assumptions of the model cannot be reconciled with the extremely large strain amplitudes arising in our experiments. The quantitative explanation of delayed solidification in Laponite therefore remains an open theoretical challenge.

Interface-Induced Anisotropy and the Nematic Glass/Gel State in Jammed Aqueous Laponite Suspensions

Aqueous suspensions of Laponite, a system composed of disklike nanoparticles, are found to develop optical birefringence over several days, well after the suspensions solidified because of jamming. The optical anisotropy is particularly enhanced near the air-Laponite suspension interface over length scales of several millimeters, which is beyond 5 orders of magnitude larger than the particle length scale, suggestive of large-scale ordering influenced by the interface. The orientational order increases with time and is always greater for higher concentration of salt, higher concentration of Laponite, and higher temperatures of the suspension. Although weakly birefringent, Laponite suspensions covered by paraffin oil do not show any enhancement in optical anisotropy near the interface compared to that in the bulk. We suggest that the expedited structure formation near the air interface propagating progressively inside the sample is responsible for the observed behavior. We discuss the observed nematic ordering in the context of glass-like and gel-like microstructure associated with aqueous Laponite suspensions.

Squeeze flow behavior of (soft glassy) thixotropic material

We study the flow behavior of a model soft glassy material − an aqueous suspension of Laponite − when it is squeezed between two circular parallel plates of different roughness. Aqueous suspension of Laponite shows a time dependent aging behavior as reflected in increased elastic modulus as well as yield stress, both of which however also decrease with an increase in the strength of deformation field thereby demonstrating typical thixotropic character. In a squeeze flow situation, under both force as well as velocity controlled modes; we find the behavior to be independent of the initial gap between the plates. In a constant force mode, the gap between the plates decreases until it reaches a finite limiting value, which is found to increase with an increase in age of the material as well as with a decrease in the applied force. In constant velocity experiments, at large gaps between the plates, normal force varies inversely with plate separation. The normal force is higher for a sample aged for a longer time as well as for a larger velocity of the top plate. We observe that the experimental behavior follows prediction of Herschel–Bulkley model solved for the squeeze flow (with different friction coefficients at the two plates) reasonably well under weak deformation fields. However, under strong deformation fields, experimental behavior deviates significantly from the prediction of Herschel–Bulkley model. This deviation arises due to melting or partial yielding of Laponite suspension under large deformation fields causing decrease in the viscosity, elastic modulus and the yield stress.