arXiv subjects

Ranjini Bandyopadhyay

Publications and source records attributed to Ranjini Bandyopadhyay.

At least 37 records · Page 2Linked to original sources

arXiv2021

Influence of dispersion medium structure on the physicochemical properties of aging colloidal suspensions investigated using the synthetic clay Laponite

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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arXiv2020

The Intriguing Flow Behavior of Soft Materials

Materials that can be deformed by thermal stresses at room temperature are called soft materials. Colloidal suspensions comprising solid particles evenly distributed in a fluid phase (smoke, fog, ink and milk, for example), emulsions(mayonnaise, lotions and creams), pastes (tomato ketchup, toothpaste), granular media (a bag of rice or sand), and polymer gels (polysaccharide gels) can be categorized as soft materials and are ubiquitous both at home and in industrial setups. Soft materials exhibit rich flow and deformation behaviors characterized by intriguing properties such as shear-thinning or thixotropy, shear-thickening or dilatancy, non-zero normal and yield stresses, etc. This article explains some of the mysterious flow properties of soft materials.

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arXiv2020

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 suspension 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 are 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.

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arXiv2020

Side branched patterns, coalescence and stable interfaces during radial displacement of a viscoelastic fluid

We explore the interfacial instability that results when a Newtonian fluid (a glycerol-water mixture, inner fluid) displaces a viscoelastic fluid (a dense cornstarch suspension, outer fluid) in a radial Hele-Shaw cell. As the ratio of viscosities of the inner and outer fluids is increased, side branched interfacial patterns are replaced by more stable interfaces that display proportionate growth and finger coalescence. We correlate the average finger spacing with the most dominant wavelength of interfacial instability, computed using a mathematical model that accounts for viscous fingering in miscible Hele-Shaw displacements. The model predictions on the role of viscosity ratio on finger spacing are in close agreement with the experimental observations. Our study lends insight into the significant contribution of the viscoelasticity of the outer fluid on the morphology and growth of interfacial patterns.

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arXiv2020

Influence of particle size on the thermoresponsive and rheological properties of aqueous poly(N-isopropylacrylamide) colloidal suspensions

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.

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arXiv2018

Electric field induced gelation in aqueous nanoclay suspensions

Aqueous colloidal Laponite clay suspensions transform spontaneously to a soft solid-like arrested state as its aging or waiting time increases. This article reports the rapid transformation of aqueous Laponite suspensions into soft solids due to the application of a DC electric field. A substantial increase in the speed of solidification at higher electric field strengths is also observed. The electric field is applied across two parallel brass plates immersed in the Laponite suspension. The subsequent solidification that takes place on the surface of the positive electrode is attributed to the dominant negative surface charges on the Laponite particles and the associated electrokinetic phenomena. With increasing electric field strength, a dramatic increase is recorded in the elastic moduli of the samples. These electric field induced Laponite soft solids demonstrate all the typical rheological characteristics of soft glassy materials. They also exhibit a two-step shear melting process similar to that observed in attractive soft glasses. The microstructures of the samples, studied using cryo-scanning electron microscopy (SEM), are seen to consist of percolated network gel-like structures, with the connectivity of the gel network increasing with increasing electric field strengths. In comparison with salt induced gels, the electric field induced gels studied here are mechanically stronger and more stable over longer periods of time

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arXiv2017

Effects of polydispersity on the glass transition dynamics of aqueous suspensions of soft spherical colloidal particles

Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) particles of a nearly constant swelling ratio and with polydispersity indices (PDIs) varying over a wide range (7.4% - 48.9%) are synthesized to study the effects of polydispersity on the dynamics of suspensions of soft PNIPAM colloidal particles. The PNIPAM particles are characterized using dynamic light scattering (DLS) and scanning electron microscopy (SEM). The zero shear viscosity ($η_{0}$) data of these colloidal suspensions, estimated from rheometric experiments as a function of the effective volume fraction $ϕ_{eff}$ of the suspensions, increases with increase in $ϕ_{eff}$ and shows a dramatic increase at $ϕ_{eff}=ϕ_{0}$. The data for $η_{0}$ as a function of $ϕ_{eff}$ fits well to the Vogel-Fulcher-Tammann (VFT) equation. It is observed that increasing PDIs results in increasingly fragile supercooled liquid-like behavior, with the parameter $ϕ_{0}$, extracted from the fits to the VFT equation, shifting towards higher $ϕ_{eff}$. The observed increase in fragility is attributed to the prevalence of dynamical heterogeneities (DHs) in these polydisperse suspensions, while the simultaneous shift in $ϕ_{0}$ is ascribed to the decoupling of the dynamics of the smallest and largest particles. Finally, it is observed that the intrinsic nonlinearity of these suspensions, estimated at the third harmonic near $ϕ_{0}$ in Fourier transform oscillatory rheological experiments, increases with increase in PDIs. Our results are in agreement with theoretical predictions and simulation results for polydisperse hard sphere colloidal glasses and clearly demonstrate that jammed suspensions of polydisperse colloidal particles can be effectively fluidized with increasing PDIs.

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arXiv2016

Study of dynamical heterogeneities in aging colloidal nanoclay suspensions

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 $α$-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.

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arXiv2015

Characteristics of the secondary relaxation process in soft colloidal suspensions

A universal secondary relaxation process, known as the Johari-Goldstein (JG) $β$-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 relationship with the $α$-relaxation process. However, the absence of a J-G $β$-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. $α$ and $β$-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 $β$-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 $β$-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 $α$-relaxation time and the stretching exponent ($β$) 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 $β$-relaxation mode for soft colloidal suspensions of Laponite.

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arXiv2015

Effect of electrolyte on the microstructure and yielding of aqueous dispersions of colloidal clay

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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arXiv2015

Kinetics of the glass transition of fragile soft colloidal suspensions

Microscopic relaxation timescales are estimated from the autocorrelation functions obtained by dynamic light scattering experiments for Laponite suspensions with different concentrations ($C_{L}$), added salt concentrations ($C_{S}$) and temperatures ($T$). It has been shown in an earlier work [Soft Matter, 10, 3292-3300 (2014)] that the evolutions of relaxation timescales of colloidal glasses can be compared with molecular glass formers by mapping the waiting time ($t_{w}$) of the former with the inverse of thermodynamic temperature ($1/T$) of the latter. In this work, the fragility parameter $D$, which signifies the deviation from Arrhenius behavior, is obtained from fits to the time evolutions of the structural relaxation timescales. For the Laponite suspensions studied in this work, $D$ is seen to be independent of $C_{L}$ and $C_{S}$, but is weakly dependent on $T$. Interestingly, the behavior of $D$ corroborates the behavior of fragility in molecular glass formers with respect to equivalent variables. Furthermore, the stretching exponent $β$, which quantifies the width $w$ of the spectrum of structural relaxation timescales is seen to depend on $t_{w}$. A hypothetical Kauzmann time $t_{k}$, analogous to the Kauzmann temperature for molecular glasses, is defined as the timescale at which $w$ diverges. Corresponding to the Vogel temperature defined for molecular glasses, a hypothetical Vogel time $t^{\infty}_α$ is also defined as the time at which the structural relaxation time diverges. Interestingly, a correlation is observed between $t_{k}$ and $t^{\infty}_α$, which is remarkably similar to that known for fragile molecular glass formers. A coupling model that accounts for the $t_{w}$-dependence of the stretching exponent is used to analyse and explain the observed correlation between $t_{k}$ and $t^{\infty}_α$.

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arXiv2014

Formation and Rupture of Ca$^{2+}$ Induced Pectin Biopolymer Gels

When calcium salts are added to an aqueous solution of polysaccharide pectin, ionic cross-links form between pectin chains, giving rise to a gel network in dilute solution. In this work, dynamic light scattering (DLS) is employed to study the microscopic dynamics of the fractal aggregates (flocs) that constitute the gels, while rheological measurements are performed to study the process of gel rupture. As calcium salt concentration is increased, DLS experiments reveal that the polydispersities of the flocs increase simultaneously with the characteristic relaxation times of the gel network. Above a critical salt concentration, the flocs become interlinked to form a reaction-limited fractal gel network. Rheological studies demonstrate that the limits of the linear rheological response and the critical stresses required to rupture these networks both decrease with increase in salt concentration. These features indicate that the ion-mediated pectin gels studied here lie in a `strong link' regime that is characterised by inter-floc links that are stronger than intra-floc links. A scaling analysis of the experimental data presented here demonstrates that the elasticities of the individual fractal flocs exhibit power-law dependences on the added salt concentration. We conclude that when pectin and salt concentrations are both increased, the number of fractal flocs of pectin increases simultaneously with the density of crosslinks, giving rise to very large values of the bulk elastic modulus.

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arXiv2014

The encapsulation of hydrophobic drugs in Pluronic F127 micelles: the effects of drug hydrophobicity, solution temperature and pH

Three drugs, Ibuprofen, Aspirin and Erythromycin, are encapsulated in spherical Pluronic F127 micelles. The shapes and the size distributions of the micelles in dilute, aqueous solutions, with and without drugs, are ascertained using cryo- Scanning Electron Microscopy and Dynamic Light Scattering (DLS) experiments, respectively. Uptake of drugs above a threshold concentration is seen to reduce the critical micellization temperature of the solution. The mean hydrodynamic radii and polydispersities of the micelles are found to increase with decrease in temperature and in the presence of drug molecules. The hydration of the micellar core at lower temperatures is verified using fluorescence measurements. Increasing solution pH leads to the ionization of the drugs incorporated in the micellar cores. This causes rupture of the micelles and release of the drugs into the solution at the highest solution pH value of 11.36 investigated here and is studied using DLS and fluorescence spectrocopy.

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arXiv2014

Use of ultrasound attenuation spectroscopy to determine the size distribution of clay tactoids in aqueous suspensions

The dispersion processes of aqueous samples of clay are studied using ultrasound attenuation spectroscopy. The attenuation spectra that are acquired in the frequency range $10-100$ MHz are used to determine the particle size distributions (PSDs) for different concentrations and ages of the clay suspensions. Our analysis, using equivalent spherical diameter (ESD) for circular discs under Stokes drag in samples of concentrations greater than 1.5\% w/v, shows that a substantial fraction of the aggregates in suspension are actually tactoids that are composed of more than one platelet. This is in contrast to the general belief that clay disperses into individual platelets in the concentration range where their suspensions exhibit glassy behavior. We conclude that the incomplete fragmentation of the clay tactoids arises from the rapid enhancement of the inter-tactoid Coulombic repulsion.

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arXiv2013

Investigation of the dynamical slowing down process in soft glassy colloidal suspensions: comparisons with supercooled liquids

The primary and secondary relaxation timescales of aging colloidal suspensions of Laponite are estimated from intensity autocorrelation functions obtained in dynamic light scattering (DLS) experiments. The dynamical slowing down of these relaxation processes are compared with observations in fragile supercooled liquids by establishing a one-to-one mapping between the waiting time since filtration of a Laponite suspension and the inverse of the temperature of a supercooled liquid that is rapidly quenched towards its glass transition temperature. New timescales, such as the Vogel time and the Kauzmann time, are extracted to describe the phenomenon of dynamical arrest in Laponite suspensions. In results that are strongly reminiscent of those extracted from supercooled liquids approaching their glass transitions, it is demonstrated that the Vogel time calculated for each Laponite concentration is approximately equal to the Kauzmann time, and that a strong coupling exists between the primary and secondary relaxation processes of aging Laponite suspensions. Furthermore, the experimental data presented here clearly demonstrates the self-similar nature of the aging dynamics of Laponite suspensions within a range of sample concentrations.

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arXiv2013

Novel Experimentally Observed Phenomena in Soft Matter

Soft materials such as colloidal suspensions, polymer solutions and liquid crystals are constituted by mesoscopic entities held together by weak forces. Their mechanical moduli are several orders of magnitude lower than those of atomic solids. The application of small to moderate stresses to these materials results in the disruption of their microstructures. The resulting flow is non-Newtonian and is characterised by features such as shear rate-dependent viscosities and non-zero normal stresses. This article begins with an introduction to some unusual flow properties displayed by soft matter. Experiments that report a spectrum of novel phenomena exhibited by these materials, such as turbulent drag reduction, elastic turbulence, the formation of shear bands and the existence of rheological chaos, flow-induced birefringence and the unusual rheology of soft glassy materials, are reviewed. The focus then shifts to observations of the liquid-like response of granular media that have been subjected to external forces. The article concludes with examples of the patterns that emerge when certain soft materials are vibrated, or when they are displaced with Newtonian fluids of lower viscosities.

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arXiv2012

Scaling behavior in the convection-driven Brazil-nut effect

The Brazil-nut effect is the phenomenon in which a large intruder particle immersed in a vertically shaken bed of smaller particles rises to the top, even when it is much denser. The usual practice, while describing these experiments, has been to use the dimensionless acceleration Γ=a ω^2/g, where a and ωare respectively the amplitude and the angular frequency of vibration and g is the acceleration due to gravity. Considering a vibrated quasi-two-dimensional bed of mustard seeds, we show here that the peak-to-peak velocity of shaking v= aω, rather than Γ, is the relevant parameter in the regime where boundary-driven granular convection is the main driving mechanism. We find that the rise-time τof an intruder is described by the scaling law τ~ (v-v_c)^{-α}, where v_c is identified as the critical vibration velocity for the onset of convective motion of the mustard seeds. This scaling form holds over a wide range of (a,ω), diameter and density of the intruder.

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arXiv2011

Experimental Studies of the Jamming Behaviour of Triblock Copolymer Solutions and Triblock Copolymer-Anionic Surfactant Mixture

Photon correlation spectroscopy and rheological measurements are performed to investigate the microscopic dynamics and mechanical responses of aqueous solutions of triblock copolymers and aqueous mixtures of triblock copolymers and anionic surfactants. Increasing the concentration of triblock copolymers results in a sharp increase in the magnitude of the complex moduli characterising the samples. This is understood in terms of the changes in the aggregation and packing behaviours of the copolymers and the constraints imposed upon their dynamics due to increased close packing. The addition of suitable quantities of an anionic surfactant to a strongly elastic copolymer solution results in a decrease in the complex moduli of the samples by several decades. It is argued that the shape anisotropy and size polydispersity of the micelles comprising mixtures cause dramatic changes in the packing behaviour, resulting in sample unjamming and the observed decrease in complex moduli. Finally, a phase diagram is constructed in the temperature-surfactant concentration plane to summarise the jamming-unjamming behaviour of aggregates constituting triblock copolymer-anionic surfactant mixtures.

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