Combined effects of nanoparticle size, and nanoparticle and surfactant concentrations on the evaporative kinetics, dried morphologies, and plasmonic property of gold colloidal dispersion droplets.

Understanding the combined influence of various parameters on the formation and morphologies of distinct solute deposit patterns obtained after droplet drying is essential for developing numerous real-time applications. In this work, gold nanoparticle (Au-NP) dispersion droplets are dried on a hydrophilic substrate and the coupled effects of nanoparticle size, and nanoparticle and surfactant (CTAB) concentrations on the evaporative kinetics and evaporation-induced nanoparticle assemblies in dried deposit patterns are studied using optical and scanning electron microscopy. The distinct stages of drying of a cetyltrimethylammonium bromide (CTAB) stabilized Au-NP dispersion droplet, such as the evolutions of pinning, depinning, and a depletion region, change drastically for a combined increase of CTAB concentration and nanoparticle size for different nanoparticle concentrations. Accordingly, the dried pattern is composed of distinct regions of closely bound ordered Au-NP assemblies coexisting with loosely bound disordered packings of Au-NPs that form inside and outside the coffee stain pattern. The multilayers of densely packed and hexagonally arranged Au-NPs at the outer coffee stain edge are tested for surface-enhanced Raman scattering activity against a standard probe molecule (Rhodamine B-RhB). The least detection limit of RhB at the outer coffee stain edge improves by three orders of magnitude with increasing nanoparticle concentrations and nanoparticle sizes. The present study demonstrates that the drying kinetics, distinct dried deposit morphologies, and the limit of plasmonic activity of the deposited Au-NPs can be fine-tuned via a combined variation of CTAB concentration, nanoparticle size, and nanoparticle concentration in the Au-NP dispersion droplet.

Correlating microscopic viscoelasticity and structure of an aging colloidal gel using active microrheology and cryogenic scanning electron microscopy.

Optical tweezers (OTs) can detect pico-Newton range forces operating on a colloidal particle trapped in a medium and have been successfully utilized to investigate complex systems with internal structures. LAPONITE® clay particles in an aqueous medium self-assemble to form microscopic networks over time as electrostatic interactions between the particles gradually evolve in a physical aging process. We investigate the forced movements of an optically trapped micron-sized colloidal probe particle, suspended in an aging LAPONITE® suspension, as the underlying LAPONITE® microstructures gradually develop. Our OT-based oscillatory active microrheology experiments allow us to investigate the mechanical responses of the evolving microstructures in aging aqueous clay suspensions of concentrations ranging from 2.5% w/v to 3.0% w/v and at several aging times between 90 and 150 minutes. We repeat such oscillatory measurements for a range of colloidal probe particle diameters and investigate the effect of probe size on the microrheology of the aging suspensions. Using cryogenic field emission scanning electron microscopy (cryo-FESEM), we examine the average pore areas of the LAPONITE® suspension microstructures for various sample concentrations and aging times. By combining our OT and cryo-FESEM data, we report here for the first time to the best of our knowledge, an inverse correlation between the crossover modulus and the average pore diameter of the aging suspension microstructures for the different suspension concentrations and probe particle sizes studied here.

Dichotomous behaviors of stress and dielectric relaxations in dense suspensions of swollen thermoreversible hydrogel microparticles.

HYPOTHESIS: While the mechanical disruption of microscopic structures in complex fluids by large shear flows has been studied extensively, the effects of applied strains on the dielectric properties of macromolecular aggregates have received far less attention. Simultaneous rheology and dielectric experiments can be employed to study the dynamics of sheared colloidal suspensions over spatiotemporal scales spanning several decades. EXPERIMENTS: Using a precision impedance analyzer, we study the dielectric behavior of strongly sheared aqueous suspensions of thermoreversible hydrogel poly(N-isopropylacrylamide) (PNIPAM) particles at different temperatures. We also perform stress relaxation experiments to uncover the influence of large deformations on the bulk mechanical moduli of these suspensions. FINDINGS: All the sheared PNIPAM suspensions exhibit distinct dielectric relaxation processes in the low and high frequency regimes. At a temperature below the lower consolute solution temperature (LCST), the complex permittivities of highly dense PNIPAM suspensions decrease with increase in applied oscillatory strain amplitudes. Simultaneously, we note a counter-intuitive slowdown of the dielectric relaxation dynamics. Contrary to our rheo-dielectric findings, our bulk rheology experiments, performed under identical conditions, reveal shear-thinning dynamics with increasing strain amplitudes. We propose the shear-induced rupture of fragile clusters of swollen PNIPAM particles to explain our observations. Our work illustrates that rheo-dielectric studies have enormous potential for providing deep insights into the length scale-dependent dynamical properties of complex systems such as dense suspensions and soft glasses.

Soft matter research in India.

Research on soft matter and biological physics has grown tremendously in India over the past decades. In this editorial, we summarize the twenty-three research papers that were contributed to the special issue on Soft matter research in India. The papers in this issue highlight recent exciting advances in this rapidly expanding research area and include theoretical studies and numerical simulations of soft and biological systems, the synthesis and characterization of novel, functional soft materials and experimental investigations of their complex flow behaviours.

DC field coupled evaporation of a sessile gold nanofluid droplet.

The coffee stain formed when a sessile nanofluid colloidal droplet dries on a substrate displays distinct nanoparticle aggregation regimes. We employ scanning electron microscopy to study the coffee stain morphologies when DC electric fields are applied to drying aqueous suspension droplets of CTAB capped gold nanorods (Au-NRs) on a hydrophilic substrate. We observe a typical coffee ring edge with several Au-NR domains due to outward capillary flow both in the absence and presence of the electric field. The Au-NRs at the coffee ring edge assemble in a smectic-like phase with homogeneous alignment in a zero DC field. Despite the presence of strong evaporation-induced flows, application of a DC electric field perpendicular to the substrate results in homeotropic alignment of the Au-NRs at the coffee ring edge. Clusters of Au-NRs with short-range order form at the inner coffee ring edge which we attribute to Marangoni eddies. Moving towards the centre of the coffee stain, we note a depletion region lacking particles, followed by non-uniform deposition of Au-NRs. Au-NR arrays are also found to deposit outside the coffee ring, presumably due to depinning of the evaporating droplet during the initial stages of droplet drying. In contrast to the outer coffee ring edge, we note no change in Au-NR orientation in other regions of the stain due to the extremely low particle concentrations. We believe that our results are applicable to assemblies of a variety of surfactant capped metal nanorods.

Influence of medium structure on the physicochemical properties of aging colloidal dispersions investigated using the synthetic clay LAPONITE®.

Physical aging in colloidal dispersions manifests as a reduction in kinetic freedom of the colloids. In aqueous dispersions of charged clay colloids, the role of interparticle electrostatic interactions in determining the aging dynamics has been evaluated extensively. Despite water being the dispersion medium, the influence of water structure on the physicochemical properties of aging clay dispersions has, however, not been considered before. In this work, we use LAPONITE®, a model hectorite clay mineral that acquires surface charges when dispersed in water, to study the relative contributions of dispersion medium structure and interparticle electrostatic interactions on the physicochemical properties of aging hectorite clay dispersions. The structure of the dispersion medium is modified either by incorporating dissociating/non-dissociating kosmotropic (structure-inducing) or chaotropic (structure-disrupting) molecules or by changing dispersion temperature. Photon correlation spectroscopy, rheological measurements and particle-scale imaging are employed to evaluate the physicochemical properties of the dispersions. Our experiments involving incorporation of external additives demonstrate a strong influence of dispersion medium structure on the dispersion properties when the interparticle electrostatic interactions are weak. We introduce a new temperature dependent measurement protocol, wherein the temperature of the medium is fixed before adding the clay particles, to manipulate the hydrogen bonds in the aqueous medium in the absence of external additives. Accelerated aging, observed upon raising the temperature regardless of the experimental thermal histories, is attributed to increased interparticle electrostatic interactions as in the room temperature experiments with ionic additives. Our study identifies that in the presence of weak interparticle electrostatic interactions, changes in the physicochemical properties of charged clay dispersions can be driven by manipulating hydrogen bond populations in aqueous medium.

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.

Study of dynamical heterogeneities in colloidal nanoclay suspensions approaching dynamical arrest.

The dynamics of aqueous Laponite clay suspensions slow down with increasing sample waiting time (t w ). This behavior, and the material fragility that results, closely resemble the dynamical slowdown in fragile supercooled liquids with decreasing temperature, and are typically ascribed to the increasing sizes of distinct dynamical heterogeneities in the sample. In this article, we characterize the dynamical heterogeneities in Laponite suspensions by invoking the three-point dynamic susceptibility formalism. The average time-dependent two-point intensity autocorrelation and its sensitivity to t w are probed in dynamic light scattering experiments. Distributions of relaxation time scales, deduced from the Kohlrausch-Williams-Watts equation, are seen to widen with increasing t w . The calculated three-point dynamic susceptibility of Laponite suspensions exhibits a peak, with the peak height increasing with evolving t w at fixed volume fraction or with increasing volume fraction at fixed t w , thereby signifying the slowdown of the sample dynamics. The number of dynamically correlated particles, calculated from the peak-height, is seen to initially increase rapidly with increasing t w , before eventually slowing down close to the non-ergodic transition point. This observation is in agreement with published reports on supercooled liquids and hard sphere colloidal suspensions and offers a unique insight into the colloidal glass transition of Laponite suspensions.

Aggregation and stability of anisotropic charged clay colloids in aqueous medium in the presence of salt.

Na-montmorillonite nanoclay is a colloid of layered mineral silicate. When dispersed in water, this mineral swells on absorption of water and exfoliates into platelets with electric double layers on their surfaces. Even at low particle concentration, the aqueous dispersion can exhibit a spontaneous ergodicity breaking phase transition from a free flowing liquid to nonequilibrium, kinetically arrested and disordered states such as gels and glasses. In an earlier publication [Applied Clay Science, 2015, 114, 8592], we showed that the stability of clay gels can be enhanced by adding a salt later to the clay dispersion prepared in deionized water, rather than by adding the clay mineral to a previously mixed salt solution. Here, we directly track the collapsing interface of sedimenting clay gels using an optical method and show that adding salt after dispersing the clay mineral does indeed result in more stable gels even in very dilute dispersions. These weak gels are seen to exhibit a transient collapse after a finite delay time, a phenomenon observed previously in depletion gels. The velocity of the collapse oscillates with the age of the sample. However, the average velocity of collapse increases with sample age up to a peak value before decreasing at higher ages. With increasing salt concentration, the delay time for transient collapse decreases, while the peak value of the collapsing velocity increases. Using ultrasound attenuation spectroscopy, rheometry and cryogenic scanning electron microscopy, we confirm that morphological changes of the gel network assembly, facilitated by thermal fluctuations, lead to the observed collapse phenomenon. Since clay minerals are used extensively in polymer nanocomposites, as rheological modifiers, stabilizers and gas absorbents, we believe that the results reported in this work are extremely useful for several practical applications and also for understanding geophysical phenomena such as the formation and stability of quicksand and river deltas.

Effect of electrolytes 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.

Kinetics of the glass transition of fragile soft colloidal suspensions.

Microscopic relaxation time scales are estimated from the autocorrelation functions obtained by dynamic light scattering experiments for Laponite suspensions with different concentrations (CL), added salt concentrations (CS), and temperatures (T). It has been shown in an earlier work [D. Saha, Y. M. Joshi, and R. Bandyopadhyay, Soft Matter 10, 3292 (2014)] that the evolutions of relaxation time scales of colloidal glasses can be compared with molecular glass formers by mapping the waiting time (tw) 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 time scales. For the Laponite suspensions studied in this work, D is seen to be independent of CL and CS 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 ß, which quantifies the width w of the spectrum of structural relaxation time scales, is seen to depend on tw. A hypothetical Kauzmann time tk, analogous to the Kauzmann temperature for molecular glasses, is defined as the time scale at which w diverges. Corresponding to the Vogel temperature defined for molecular glasses, a hypothetical Vogel time tα (∞) is also defined as the time at which the structural relaxation time diverges. Interestingly, a correlation is observed between tk and tα (∞), which is remarkably similar to that known for fragile molecular glass formers. A coupling model that accounts for the tw-dependence of the stretching exponent is used to analyse and explain the observed correlation between tk and tα (∞).

Dynamic light scattering study and DLVO analysis of physicochemical interactions in colloidal suspensions of charged disks.

The interparticle interactions in colloidal suspensions of charged disks of Laponite clay in water were investigated using dynamic light scattering (DLS) and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. We studied the effects of clay concentration (C(L)), the concentration of externally added salt (C(S)), and temperature (T) on the microscopic dynamics of the clay suspensions. The fast (τ1) and mean slow relaxation times (⟨τ(ww)⟩) of Laponite suspensions were extracted from intensity autocorrelation functions measured at different waiting times (t(w)) after sample preparation. Comprehensive Laponite concentration-salt concentration-temperature-time superpositions of both the microscopic diffusive time scales and the stretching exponent corresponding to the slow relaxation process highlight the self-similar nature of the energy landscapes of the Laponite suspensions. The evolution of the sodium ion concentration in the aging suspension with tw, measured for several values of CL, CS, and T, was used in a DLVO analysis of the free energy of the suspension for two charged disks parallely approaching one another. This analysis confirms that, in addition to repulsive interparticle interactions, attractive interactions also play a pivotal role in the microscopic dynamics of spontaneously evolving Laponite suspensions.

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 carried out to study the process of gel rupture. As the calcium salt concentration is increased, DLS experiments reveal that the polydispersity 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 the 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 both pectin and salt concentrations are 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.

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 associated with primary and secondary relaxation processes, such as the characteristic timescale associated with the slowdown of the secondary relaxation process and the glass transition 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 a strong coupling exists between the primary and secondary relaxation processes of aging Laponite suspensions in the cage-forming regime. Furthermore, the experimental data presented here clearly demonstrate the self-similar nature of the aging dynamics of Laponite suspensions within a range of sample concentrations.

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 intertactoid Coulombic repulsion.

Encapsulation of hydrophobic drugs in Pluronic F127 micelles: 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.

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 = aω(2)/g, where a and ω are, 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 τ of 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.