Tribological and Rheological Study of Thixotropic Gels of 2D Nanoparticles.

A thixotropic colloidal gel constituting an aqueous dispersion of synthetic clay Laponite with varying concentrations of salt has been studied for its rheological and tribological performance as a lubricant. We observed that the incorporation of NaCl induces notable enhancements in the colloidal gel's relaxation time, elastic modulus, and yield stress. Although an increase in NaCl concentration decreases the material's relaxation time dependence on waiting time (tw), overall, the strength of its thixotropic character has been observed to increase with an increase in salt concentration. The analysis of friction and wear indicated that the utilization of a thixotropic colloidal gel of Laponite with a higher concentration of NaCl resulted in progressively greater reductions in both the coefficient of friction and specific wear rates under various load-speed conditions. Severe abrasive wear on disc surface under dry test, gradually mitigated upon the introduction of these lubricants. Two simultaneous lubricating mechanisms, first, the smooth sliding of the friction pair, facilitated by the alignment of Laponite particles in the direction of shear forces, and second, the stable structure of Laponite, coupled with the addition of NaCl, enabling continuous replenishment of the wear track with lubricant, are attributed to lubrication effectiveness.

Large amplitude oscillatory shear study of a colloidal gel near the critical state.

A system undergoing sol-gel transition passes through a unique point, known as the critical gel state, where it forms the weakest space spanning percolated network. We investigate the nonlinear viscoelastic behavior of a colloidal dispersion at the critical gel state using large amplitude oscillatory shear rheology. The colloidal gel at the critical point is subjected to oscillatory shear flow with increasing strain amplitude at different frequencies. We observe that the first harmonic of the elastic and viscous moduli exhibits a monotonic decrease as the material undergoes a linear to nonlinear transition. We analyze the stress waveform across this transition and obtain the nonlinear moduli and viscosity as a function of frequency and strain amplitude. The analysis of the nonlinear moduli and viscosities suggests intracycle strain stiffening and intracycle shear thinning in the colloidal dispersion. Based on the insights obtained from the nonlinear analysis, we propose a potential scenario of the microstructural changes occurring in the nonlinear region. We also develop an integral model using the time-strain separable Kaye-Bernstein-Kearsley-Zapas constitutive equation with a power-law relaxation modulus and damping function obtained from experiments. The proposed model with a slight adjustment of the damping function inferred using a spectral method, compares well with experimental data at all frequencies.

Signatures of Overaging in an Aqueous Dispersion of Carbopol.

In this work, we study the effect of the deformation field on the physical aging behavior of an aqueous Carbopol dispersion. It is composed of soft swollen particles of gel that get deformed and acquire a polygonal shape, with flat interfaces rendering the dispersion a soft solid-like consistency as filled volume fraction approaches unity. It has been proposed that owing to release of stored elastic energy in the deformed particles, Carbopol dispersion undergoes microstructural evolution that is reminiscent of physical aging in soft glassy materials. We observe that application of moderate magnitude of oscillatory strain to Carbopol dispersion slows down its relaxation dynamics, thereby showing characteristics of overaging. On the other hand, the sufficiently high magnitude of strain makes the relaxation dynamics faster, causing rejuvenation. We also solve the soft glassy rheology model, which, when subjected to the same flow field, corroborates with experimental observations on the Carbopol dispersion. This behavior, therefore, suggests that in a system of jammed soft particles of Carbopol, the particles occupying shallow energy wells upon application of moderate strain field adjust themselves in such a manner that they predominantly occupy the deeper energy wells leading to observe the overaging dynamics.

Rheological Behavior and in Situ Confocal Imaging of Bijels Made by Mixing.

Bijels (bicontinuous interfacially jammed emulsion gels) have the potential to be useful in many different applications due to their internal connectivity and the possibility of efficient mass transport through the channels. Recently, new methods of making the bijel have been proposed, which simplify the fabrication process, making commercial application more realistic. Here, we study the flow properties of bijels prepared by mixing alone using oscillatory rheology combined with confocal microscopy and also squeezing flow experiments. We found that the bijel undergoes a two-step yielding process where the first step corresponds to the fluidizing of the interface, allowing the motion of the structure, and the second step corresponds to the breaking of the structure. In the squeeze flow experiments, the yield stress of the bijel is observed to show a power law dependence on squeezing speed. However, when stress in excess of yield stress is plotted against shear rate, all the different squeeze flow data show a superposition.

Three-dimensional yielding in anisotropic materials: validation of Hill's criterion.

Yielding transition in isotropic soft materials under the superposition of orthogonal deformation fields is known to follow von Mises' criterion. However, in anisotropic soft materials, von Mises' criterion fails owing to the preferred directions associated with the system. In this work we study a model anisotropic yield stress system: electrorheological (ER) fluids which show structural formation in the direction of an electric field. We subject the ER fluids to the superposition of orthogonal stress fields which leads to different yield stress values. We obtain a yielding state diagram by plotting the normalized rotational shear stress against the normalized radial shear stress corresponding to a yield point for a given electric field. Remarkably, the state diagram validates the Hill yielding criterion, which is a general yielding criterion for materials with anisotropy along three orthogonal directions, originally developed for metallic systems. Validation of Hill's criterion suggests the universality of its application in anisotropic systems including conventional anisotropic soft materials having yield stress.

Adhesion strength and viscoelastic properties of polydimethylsiloxane (PDMS) based elastomeric nanocomposites with embedded electrospun nanofibers.

In the present study, the adhesive and viscoelastic properties of polydimethylsiloxane (PDMS) based nanocomposite pressure sensitive adhesives (PSAs) with embedded electrospun polyacrylonitrile (PAN) and polyvinyl alcohol (PVA) nanofibers as fillers were investigated. PDMS nanocomposite adhesive films using PAN and PVA nanofibers were synthesized by dispersing fillers in the matrix by a solvent mixing process. The adhesion strength and reusability of the prepared nanocomposite PSA films were measured using peel tests as the fraction of nanofibers in the polymer matrix is increased. The variations of the adhesive properties of the PSAs as function of the type and loading of filler were related to their rheological properties in terms of shear and elastic moduli. Although 3-fold enhancement of the adhesion strength was achieved with 0.5 wt% loading for both types (PAN and PVA) of nanocomposites as compared to elastic PDMS, the composite adhesive with PAN nanofibers can provide a superior balance of rheological properties, resulting in improved reusability over other PSAs. The differences in the adhesion and viscoelastic properties of the composite PSAs are attributed to the polymer chemistry, processability, and architecture of the electrospun nanofibers in the soft PDMS matrix.

Microstructure and Soft Glassy Dynamics of an Aqueous Laponite Dispersion.

Synthetic hectorite clay Laponite RD/XLG is composed of disk-shaped nanoparticles that acquire dissimilar charges when suspended in an aqueous medium. Owing to their property to spontaneously self-assemble, Laponite is used as a rheology modifier in a variety of commercial water-based products. In particular, an aqueous dispersion of Laponite undergoes a liquid-to-solid transition at about 1 vol % concentration. The evolution of the physical properties as the dispersion transforms to the solid state is reminiscent of physical aging in molecular as well as colloidal glasses. The corresponding soft glassy dynamics of an aqueous Laponite dispersion, including the rheological behavior, has been extensively studied in the literature. In this feature article, we take an overview of recent advances in understanding soft glassy dynamics and various efforts taken to understand the peculiar rheological behavior. Furthermore, the continuously developing microstructure that is responsible for the eventual formation of a soft solid state that supports its own weight against gravity has also been a topic of intense debate and discussion. In particularly, extensive experimental and theoretical studies lead to two types of microstructures for this system: an attractive gel-like or a repulsive glass-like structure. We carefully examine and critically analyze the literature and propose a state (phase) diagram that suggests an aqueous Laponite dispersion to be present in an attractive gel state.

Making Nonsticky Surfaces of Sticky Materials: Self-Organized Microtexturing of Viscoelastic Elastomeric Layers by Tearing.

Fabrication of large area, multiscale microtextured surfaces engineered for antiadhesion properties remains a challenge. Compared to an elastic surface, viscoelastic solids show much higher surface stickiness, tack, and adhesion owing to the increased contact area and energy dissipation. Here, we show a simple, low cost, large-area and high throughput method with roll-to-roll compatibility to fabricate multiscale, rough microstructures resistant to adhesion in a viscoelastic layer by controlled tearing of viscous film. Even a high adhesive strength viscoelastic solid layer, such as partially cured PDMS, is made nonsticky simply by its controlled tearing. The torn surface shows a fracture induced, self-organized leaflike micropattern resistant to sticking. The topography and adhesion strength of these structures are readily tuned by changing the tearing speed and the film thickness. The microtexture displays a springlike recovery, low adhesive strength, and easy release properties even under the high applied loads.

To study surface and sub-surface nanomechanical properties of electrospun polyacrylonitrile (PAN) nanofibers/polydimethylsiloxane (PDMS) composites.

We investigate surface and sub-surface nanomechanical properties of nanocomposites based on a crosslinked polydimethylsiloxane (PDMS) elastomer and electrospun polyacrylonitrile (PAN) nanofibers. Fabrication of PDMS substrates with anisotropy with respect to surface elasticity and their characterization in terms of local nanomechanical properties are important for many areas of adhesion applications. PDMS nanocomposite substrates with variations in surface elasticity over large areas are prepared by controllably embedding electrospun PAN nanofibers (∼600 nm) in a PDMS matrix using the solution casting technique. Variations of local surface stiffness properties of prepared composites are measured using force spectroscopy and force mapping modes of atomic force microscopy and compared with their macroscopic (bulk) mechanical properties. Since the surface of the prepared nanocomposite is elastically non-homogeneous, our studies are mainly focused on the investigation of the hysteresis (plasticity index) between loading and unloading curves which is a measure of energy dissipation in AFM indentation experiments. The distribution of the local plasticity index in the PAN/PDMS composites is related to the specific organization of electrospun nanofibers at the surface and sub-surface layers of the PDMS matrix. We observed that embedding 0.1-1% PAN nanofibers induces anti-plasticization effects for lower (0.1%) and higher (1%) concentrations of PAN nanofibers which represent the formation of interpenetrating networks and mat-like blended structures of PAN nanofibers within the PDMS matrix.

Phase Behavior of Aqueous Suspension of Laponite: New Insights with Microscopic Evidence.

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 suspension, 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 wt %) 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 postgel state clearly show the presence of a percolated network formed by interparticle bonds. The present work therefore conclusively establishes the system to be in an attractive gel state resolving a long-standing debate in the literature.

Analyzing a fractal gel of charged oblate nanoparticles in a suspension using time-resolved rheometry and DLVO theory.

The disk-like nanoparticles of LAPONITE® are known to self-assemble to form a fractal gel within hours after a sufficiently large concentration of LAPONITE® is dispersed in water containing salt. The concentration of sodium counterions associated with LAPONITE® particles, however, continues to increase over a period of days, suggesting that delamination of LAPONITE® disks from stacks is sluggish and/or dissociation of counterions is slow. In either case, spontaneous self-assembly of LAPONITE® particles occurs even though delamination and/or counterion dissociation has not reached its equilibrium state. In order to determine the nature of the fractal gel as the extent of delamination and/or dissociation progresses towards equilibrium, we subject the LAPONITE® suspension to a freezing-defrosting cycle, which interestingly reinitiates the gelation process in suspension afresh. Application of time-resolved rheometry to a defrosted suspension shows that iso-frequency loss tangent curves intersect at an identical point, validating the Winter-Chambon criterion for a critical fractal gel state. Interestingly, while the time required to form a critical gel is observed to decrease with increased time elapsed since preparation, at which freezing-defrosting is carried out, the fractal dimension of the critical gel is observed to remain unaffected. We also solve DLVO theory for free energy interactions between the negatively charged LAPONITE® particle faces and analyze the observed phenomena.

Passive microrheology in the effective time domain: analyzing time dependent colloidal dispersions.

We studied the aging dynamics of an aqueous suspension of LAPONITE®, a model time dependent soft glassy material, using a passive microrheology technique. This system is known to undergo physical aging during which its microstructure evolves progressively to explore lower free energy states. Optical microscopy is used to monitor the motion of micron-sized tracer probes embedded in a sample kept between two glass plates. The mean square displacements (MSD) obtained from the motion of the tracer particles show a systematic change from a purely diffusive behavior at short aging times to a subdiffusive behavior as the material ages. Interestingly, the MSDs at all the aging times as well as different LAPONITE® concentrations superpose remarkably to show a time-aging time master curve when the system is transformed from the real time domain to the effective time domain, which is obtained by rescaling the material clock to account for the age dependent relaxation time. The transformation of the master curve from the effective time domain to the real time domain leads to the prediction of the MSD in real time over a span of 5 decades when the measured data at individual aging times are only over 2 decades. Since the MSD obtained from microrheology is proportional to the creep compliance of a material, by using the Boltzmann superposition principle along with the convolution relation in the effective time domain, we predict the stress relaxation behavior of the system in real time. This work shows that the effective time approach applied to microrheology facilitates the prediction of long time creep and relaxation dynamics of a time dependent soft material by carrying out short time experiments at different aging times.

Analyzing aging under oscillatory strain field through the soft glassy rheology model.

In this work, we solve the Soft Glassy Rheology (SGR) model under application of oscillatory deformation field with varying magnitudes of strain as well as frequency for different noise temperatures. In the glassy domain, the SGR model undergoes time evolution of elastic modulus. Increase in strain magnitude beyond the linear regime is observed to enhance the rate of aging as manifested by a faster evolution of elastic modulus with increase in strain amplitude due to overaging. However at higher strain magnitudes, the rejuvenation effect starts dominating over the aging, thereby reducing the rate at which elastic modulus evolves. We also plot the aging phase diagram describing an occurrence of the linear, the overaging, and the rejuvenation regimes as a function of strain and frequency for different noise temperatures. The aging phase diagram suggests that while the linear regime remains unaffected by the changes in frequency and noise temperature, the width of the overaging regime increases with increase in frequency and noise temperature. We also study the time evolution of the shapes of relaxation time spectra as a function of strain amplitude, which renders further insight into the overaging and the rejuvenation behavior. While the phenomenon of overaging is observed to be an inherent character of the SGR model, experimentally not all the materials demonstrate overaging. Such a discrepancy suggests that the energy well depths before and after a yielding event may not be completely uncorrelated as assumed in the SGR formalism.

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.

A model for aging under deformation field, residual stresses and strains in soft glassy materials.

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 an inverse of characteristic relaxation time suggesting that greater mobility of the constituents induces faster aging in a material. A dependence of relaxation time on free energy is proposed, which under quiescent conditions leads to a 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 the material undergoes aging and approaches a rejuvenated state under the application of a deformation field. In particular, the model proposes distinctions between various kinds of rheological effects for different combinations of parameters. Interestingly, when the relaxation time evolution is stronger than linear, the model predicts various features observed in soft glassy materials such as thixotropic and constant yield stress, thixotropic shear banding, and the presence of residual stress and strain.

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 (∞).

Linear viscoelasticity of soft glassy materials.

Owing to lack of time translational invariance, aging soft glassy materials do not obey fundamental principles of linear viscoelasticity. We show that by transforming the linear viscoelastic framework from a real time domain into an effective time domain, wherein the material clock is readjusted to account for evolution of relaxation time, the soft glassy materials obey effective time translational invariance. Consequently, we demonstrate successful validation of principles of linear viscoelasticity (the Boltzmann superposition principle and a convolution relation for creep compliance and stress relaxation modulus) for different types of soft glassy materials in the effective time domain.

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.