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 a
lso 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 suspensi
on, 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.
A universal secondary relaxation process, known as the Johari-Goldstein (JG) $beta$-relaxation process, appears in glass formers. It involves all parts of the molecule and is particularly important in glassy systems because of its very close relation
ship with the $alpha$-relaxation process. However, the absence of a J-G $beta$-relaxation mode in colloidal glasses raises questions regarding its universality. In the present work, we study the microscopic relaxation processes in Laponite suspensions, a model soft glassy material, by dynamic light scattering (DLS) experiments. $alpha$ and $beta$-relaxation timescales are estimated from the autocorrelation functions obtained by DLS measurements for Laponite suspensions with different concentrations, salt concentrations and temperatures. Our experimental results suggest that the $beta$-relaxation process in Laponite suspensions involves all parts of the constituent Laponite particle. The ergodicity breaking time is also seen to be correlated with the characteristic time of the $beta$-relaxation process for all Laponite concentrations, salt concentrations and temperatures. The width of the primary relaxation process is observed to be correlated with the secondary relaxation time. The secondary relaxation time is also very sensitive to the concentration of Laponite. We measure primitive relaxation timescales from the $alpha$-relaxation time and the stretching exponent ($beta$) by applying the coupling model for highly correlated systems. The order of magnitude of the primitive relaxation time is very close to the secondary relaxation time. These observations indicate the presence of a J-G $beta$-relaxation mode for soft colloidal suspensions of Laponite.
Aging amorphous polymeric materials undergo free volume relaxation, which causes slowing down of the relaxation dynamics as a function of time. The resulting time dependency poses difficulties in predicting their long time physical behavior. In this
work, we apply effective time domain approach to the experimental data on aging amorphous polymers and demonstrate that it enables prediction of long time behavior over the extraordinary time scales. We demonstrate that, unlike the conventional methods, the proposed effective time domain approach can account for physical aging that occurs over the duration of the experiments. Furthermore, this procedure successfully describes time temperature superposition and time stress superposition. It can also allow incorporation of varying dependences of relaxation time on aging time as well as complicated but known deformation history in the same experiments. This work strongly suggests that the effective time domain approach can act as an important tool to analyze the long time physical behavior of aging amorphous polymeric materials. Aging amorphous polymeric materials undergo free volume relaxation, which causes slowing down of the relaxation dynamics as a function of time. The resulting time dependency poses difficulties in predicting their long time physical behavior. In this work, we apply effective time domain approach to the experimental data on aging amorphous polymers and demonstrate that it enables prediction of long time behavior over the extraordinary time scales. We demonstrate that, unlike the conventional methods, the proposed effective time domain approach can account for physical aging that occurs over the duration of the experiments. Furthermore, this procedure successfully describes time temperature superposition and time stress superposition.
In this work we conduct a transient heat conduction experiment with an aqueous suspension of nanoparticle disks of Laponite JS, a sol forming grade, using laser light interferometry. The image sequence in time is used to measure thermal diffusivity a
nd thermal conductivity of the suspension. Imaging of the temperature distribution is facilitated by the dependence of refractive index of the suspension on temperature itself. We observe that with the addition of 4 volume % of nano-disks in water, thermal conductivity of the suspension increases by around 30%. A theoretical model for thermal conductivity of the suspension of anisotropic particles by Fricke as well as by Hamilton and Crosser explains the trend of data well. In turn, it estimates thermal conductivity of the Laponite nanoparticle itself, which is otherwise difficult to measure in a direct manner. We also measure viscosity of the nanoparticle suspension using a concentric cylinder rheometer. Measurements are seen to follow quite well, the theoretical relation for viscosity of suspensions of oblate particles that includes up to two particle interaction. This result rules out the presence of clusters of particles in the suspension. The effective viscosity and thermal diffusivity data show that the shape of the particle has a role in determining enhancement of thermophysical properties of the 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.
We study diffusion of heat in an aqueous suspension of disc shaped nanoparticles of Laponite, which has finite elasticity and paste-like consistency, by using the Mach-Zehnder interferometer. We estimate the thermal diffusivity of the suspension by c
omparing the experimentally obtained temperature distribution to that with analytical solution. We observe that despite highly constrained Brownian diffusivity of particles owing to its soft glassy nature, suspensions at very small concentrations of Laponite demonstrates significant enhancement in thermal diffusivity. We correlate the observed enhancement with the possible microstructures of the Laponite suspension.
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 isothe
rmal 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 suspension of nanoclay Laponite undergoes structural evolution as a function of time, which enhances its elasticity and relaxation time. In this work we employ effective time approach to investigate long term relaxation dynamics by carrying o
ut creep experiments. Typically we observe that the monotonic evolution of elastic modulus shifts to lower aging times while maxima in viscous modulus gets progressively broader for experiments carried out on a later date since preparation (idle time) of nanoclay suspension. Application of effective time theory produces superposition of all the creep curves irrespective of their initial state. The resulting dependence of relaxation time on aging time shows very strong hyper aging dynamics at small idle times, which progressively weakens to demonstrate linear dependence in the limit of very large idle times. Remarkably this behavior of nanoclay suspension 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 progressively low energy state in the limit of very large 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 nano-clay suspensions.
