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Register a new userInfluence of dispersion medium structure on the physicochemical properties of aging colloidal suspensions investigated using the synthetic clay Laponite
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Hypothesis: Aging in colloidal suspensions manifests as a reduction in kinetic freedom of the colloids. In aqueous suspensions of charged colloids, the role of inter-particle electrostatics interactions on the aging dynamics is well debated. Despite water being the dispersion medium, the influence of water structure on the physicochemical properties of aging colloids has never been considered before. Laponite, a model hectorite clay, could be used to evaluate the relative contributions of medium structure and electrostatics in determining the physicochemical properties of aging colloidal suspensions. Experiments: The structure of the dispersion medium is modified either by incorporating uncharged/charged kosmotropic (structure-inducing) or chaotropic (structure-disrupting) molecules or by changing suspension temperature. A new protocol, wherein the medium is heated before adding clay particles, is also introduced to evaluate the effects of hydrogen bond disruptions on suspension aging. Dynamic light scattering, rheological measurements and particle-scale imaging are employed to evaluate the physicochemical properties of the suspensions. Findings: A strong influence of medium structure is evident when inter-particle electrostatic interactions are weak. Enhancement and disruption of hydrogen bonds in the medium are, respectively, strongly correlated with acceleration and delay of suspension aging dynamics. The physicochemical properties of charged clay colloidal suspensions are therefore controlled by altering hydrogen bonding in the dispersion medium.
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An aqueous suspension of the synthetic clay Laponite undergoes a transition from a liquid-like ergodic state to a glass-like nonergodic arrested state. In an observation that closely resembles the dynamical slowdown observed in supercooled liquids, the phenomenon of kinetic arrest in Laponite suspensions is accompanied by a growth in the $alpha$-relaxation time with increasing sample aging time, $t_{w}$. The ubiquitous dynamic slowdown and fragile behavior observed in glass forming liquids approaching the glass transition is typically ascribed to the growth in the size of distinct dynamical heterogeneities. In this article, we present the characterization of the dynamical heterogeneities in aging colloidal Laponite clay systems by invoking the three-point dynamic susceptibility formalism. The average time-dependent two-point intensity autocorrelation and its sensitivity to the control parameter $t_{w}$ are probed in dynamic light scattering experiments. Distributions of relaxation time scales deduced from Kohlrausch-Williams-Watts equation widen with increasing $t_{w}$ signifying the heterogeneous dynamic slowdown. A suitable formalism to calculate three-point correlation function is employed for aging colloidal suspension where the main control parameter is $t_{w}$. The calculated three-point dynamic susceptibility exhibits a peak, with the peak height increasing with evolving $t_{w}$. The number of dynamically correlated particles is seen to initially increase with increasing $t_{w}$ at a fast rate, before eventually slowing down close to the non-ergodic transition point.This observation is in agreement with reports on supercooled liquids. Our study confirms the growth of dynamical heterogeneities in suspensions of Laponite, thereby shedding new light on the fragile supercooled liquid-like dynamics of aging suspensions of these anisotropic, charged, colloidal clay nanoparticles.
We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerably reduced as compared to the prediction based on the primitive model. When these forces are repulsive, the long-distance behaviour can be described by an effective Yukawa pair potential with a solvent-renormalized charge. As a function of colloidal volume fraction and added salt concentration, this solvent-renormalized charge behaves qualitatively similar to that obtained via the Poisson-Boltzmann cell model but there are quantitative differences. For divalent counterions and nano-sized colloids, on the other hand, the hydration may lead to overscreened colloids with mutual attraction while the primitive model yields repulsive forces. All these new effects can be accounted for through a solvent-averaged primitive model (SPM) which is obtained from the full model by integrating out the solvent degrees of freedom. The SPM was used to access larger colloidal particles without simulating the solvent explicitly.
Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) particles of different sizes are synthesized by varying the concentration of sodium dodecyl sulphate (SDS) in a one-pot method. The sizes, size polydispersities and the thermoresponsivity of the PNIPAM particles are characterized by using dynamic light scattering and scanning electron microscopy. It is observed that the sizes of these particles decrease with increase in SDS concentration. Swelling ratios of PNIPAM particles measured from the thermoresponsive curves are observed to increase with decrease in particle size. This observation is understood by minimizing the Helmholtz free energy of the system with respect to the swelling ratio of the particles. Finally, the dynamics of these particles in jammed aqueous suspensions are investigated by performing rheological measurements.
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 out 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.
Na-montmorillonite is a natural clay mineral and is available in abundance in nature. The aqueous dispersions of charged and anisotropic platelets of this mineral exhibit non-ergodic kinetically arrested states ranging from soft glassy phases dominated by interparticle repulsions to colloidal gels stabilized by salt induced attractive interactions. When the salt concentration in the dispersing medium is varied systematically, viscoelasticity and yield stress of the dispersion show non-monotonic behavior at a critical salt concentration, thus signifying a morphological change in the dispersion microstructures. We directly visualize the microscopic structures of these kinetically arrested phases using cryogenic scanning electron microscopy. We observe the existence of honeycomb-like network morphologies for a wide range of salt concentrations. The transition of the gel morphology, dominated by overlapping coin (OC) and house of cards (HoC) associations of clay particles at low salt concentrations to a new network structure dominated by face-face coagulation of platelets, is observed across the critical salt concentration. We further assess the stability of these gels under gravity using electroacoustics. This study, performed for concentrated clay dispersions for a wide concentration range of externally added salt, is useful in our understanding of many geophysical phenomena that involve the salt induced aggregation of natural clay minerals.
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