A model is proposed that considers aging and rejuvenation in a soft glassy material as respectively a decrease and an increase in free energy. The aging term is weighted by inverse of characteristic relaxation time suggesting greater mobility of the
constituents induce faster aging in a material. A dependence of relaxation time on free energy is proposed, which under quiescent conditions, leads to power law dependence of relaxation time on waiting time as observed experimentally. The model considers two cases namely, a constant modulus when aging is entropy controlled and a time dependent modulus. In the former and the latter cases the model has respectively two and three experimentally measurable parameters that are physically meaningful. Overall the model predicts how material undergoes aging and approaches rejuvenated state under application of deformation field. Particularly model proposes distinction between various kinds of rheological effects for different combinations of parameters. Interestingly, when relaxation time evolves stronger than linear, the model predicts various features observed in soft glassy materials such as thixotropic and constant yield stress, thixotropic shear banding, and presence of residual stress and strain.
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.
Physical properties of out of equilibrium soft materials depend on time as well as deformation history. In this work we propose to transform this major shortcoming into gain by applying controlled deformation field to tailor the rheological propertie
s. We take advantage of the fact that deformation field of a certain magnitude can prevent particles in an aging soft glassy material from occupying energy wells up to a certain depth, thereby populating only the deeper wells. We employ two soft glassy materials with dissimilar microstructures and demonstrate that increase in strength of deformation field while aging leads to narrowing of spectrum of relaxation times. We believe that, in principle, this philosophy can be universally applied to different kinds of glassy materials by changing nature and strength of impetus.
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.
When subjected to large amplitude oscillatory shear stress, aqueous Laponite suspensions show an abrupt solidification transition after a long delay time tc. We measure the dependence of tc on stress amplitude, frequency, and on the age-dependent ini
tial 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 {gamma}0 each element can be classified as fluid or solid according to whether its local yield strain exceeds {gamma}0. 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({gamma}0) of a fluid elements becoming solid. As the fraction of solid elements builds up, {gamma}0 falls (at constant stress amplitude), so R({gamma}0) 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.
Soft glassy materials are out of thermodynamic equilibrium and show time dependent slowing down of the relaxation dynamics. Under such situation these materials follow Boltzmann superposition principle only in the effective time domain, wherein time
dependent relaxation processes are scaled by a constant relaxation time. In this work we extend effective time framework to successfully demonstrate time - temperature superposition of creep and stress relaxation data of a model soft glassy system comprised of clay suspension. Such superposition is possible when average relaxation time of the material changes with time and temperature without affecting shape of the spectrum. We show that variation in relaxation time as a function of temperature facilitates prediction of long and short time rheological behavior through time - temperature superposition from the experiments carried out over experimentally accessible timescales.
