Laponite Suspensions Research Articles

Containment strategy for subsurface H2 storage based on time-dependent soft solids

We propose an innovative containment strategy based on time-dependent soft solids, namely 2 wt% Laponite suspensions, to reinforce natural subsurface seals and engineer flow barriers, with an eye toward making H2 subsurface storage scalable and geographically agnostic. This suspension can be injected at its initial low viscosity and elasticity into a porous medium, allowing for easy pumping and targeted delivery. Once inside the target zone, it matures into a soft solid with much higher viscosity and elasticity, acting as a potential flow barrier. We discuss the rheological properties of the suspensions and demonstrate that hydrogen does not adversely affect their microstructure, but rather increases the suspensions’ viscosity and elasticity. Moreover, the suspensions enhance the rock samples’ compressive strength, while hydrogen exposure increases their stiffness and ductility. The ability of rock samples saturated with the suspensions to contain higher injected gas pressures is enhanced by aging at higher temperatures.

Thixotropy, antithixotropy, and viscoelasticity in hysteresis

Thixotropy, antithixotropy, and viscoelasticity are three types of time-dependent dynamics that involve fundamentally different underlying physical processes. Here, we show that the three dynamics exhibit different signatures in hysteresis by examining the fingerprints of the simplest thixotropic kinetic model, a new antithixotropic model that we introduce here, and the Giesekus model. We start by showing that a consistent protocol to generate hysteresis loops is a discrete shear-rate controlled ramp that begins and ends at high shear rates, rather than at low shear rates. Using this protocol, we identify two distinguishing features in the resulting stress versus shear rate loops. The first is the direction of the hysteresis loops: clockwise for thixotropy, but counterclockwise for viscoelasticity and antithixotropy. A second feature is achieved at high ramping rates where all responses lose hysteresis: the viscoelastic response shows a stress plateau at low shear rates due to lack of stress relaxation, whereas the thixotropic and antithixotropic responses are purely viscous with minimal shear thinning or thickening. We establish further evidence for these signatures by experimentally measuring the hysteresis of Laponite suspensions, carbon black suspensions, and poly(ethylene oxide) solutions, each representing a historically accepted example of each class of material behavior. The signatures measured in experiments are consistent with those predicted by the three models. This study reveals different fingerprints in hysteresis loops associated with thixotropy, antithixotropy, and viscoelasticity, which may be helpful in distinguishing the three time-dependent responses.

PH regulated desiccation crack network: A versatile template for Transparent Conducting Sheet fabrication

Abstract A novel technique of designing network templates for Transparent Conducting Sheet (TCS) has been achieved by careful modulation of pH of a desiccating colloidal suspension. The pH of aqueous Laponite suspension was changed from 7.8 to 12.7 to obtain vivid changes in the geometry and connectivity of the resultant crack network. Micron sized graphite powder compacted by slow uniform evaporation forms the conducting network on glass after the dry clay is removed completely. The resistance, transmittance, reflectance and Figure of Merit of the TCSs have been calibrated as functions of colloidal pH. The electrical and optical properties of the TCSs have been correlated to the topological measure Euler Characteristic and tortuosity of the network. The graphite on glass TCS show selective transmittance at certain pH values. The work demonstrates a cheap versatile option of TCS fabrication that shall find useful applications.

Resolving Salt-Induced Agglomeration of Laponite Suspensions Using X-ray Photon Correlation Spectroscopy and Molecular Dynamics Simulations.

Linking the physics of the relaxation behavior of viscoelastic fluids as they form arrested gel states to the underlying chemical changes is essential for developing predictive controls on the properties of the suspensions. In this study, 3 wt.% laponite suspensions are studied as model systems to probe the influence of salt-induced relaxation behavior arising from the assembly of laponite nanodisks. X-ray Photon Correlation Spectroscopy (XPCS) measurements show that laponite suspensions prepared in the presence of 5 mM concentrations of CaCl2, MgCl2 and CsCl salts accelerate the formation of arrested gel states, with CaCl2 having a significant impact followed by CsCl and MgCl2 salts. The competing effects of ion size and charge on relaxation behavior are noted. For example, the relaxation times of laponite suspensions in the presence of Mg2+ ions are slower compared to Cs+ ions despite the higher charge, suggesting that cation size dominates in this scenario. The faster relaxation behavior of laponite suspensions in the presence of Ca2+ ions compared to Cs+ ions shows that a higher charge dominates the size of the ion. The trends in relaxation behavior are consistent with the cluster formation behavior of laponite suspensions and the electrostatic interactions predicted from MD simulations. Charge balance is achieved by the intercalation of the cations at the negatively charged surfaces of laponite suspensions. These studies show that the arrested gel state of laponite suspensions is accelerated in the presence of salts, with ion sizes and charges having a competing effect on relaxation behavior.

Studying the aging of Laponite suspensions using extensional rheology

The effect of aging on the break-up dynamics of Laponite suspensions was studied in an extensional geometry. It was found that samples of increased age undergo stronger necking at the midpoint. The thinning of samples, driven purely by motion of the plates, was compared with standard shear rheology to understand how the dynamics are related to the sample properties. The Laponite suspensions exhibit a growing stress overshoot with monotonically decreasing yield strain as they age. However, it is shown that the thinning curves in extension are only a good indicator of the sample’s static yield stress, being insensitive to its yield strain. These measurements suggest that following an initial linear visco-elastic regime, samples accumulate significant plastic deformations prior to the complete yielding of the sample. The implications of this for the importance of assessing changes to the ductile—brittle nature of samples are also discussed.Graphical abstract

Experimental evidence of the effect of aging on the yielding and pre-yielding behavior of bentonite and laponite suspensions

Thixotropic yield stress materials show a shear-induced solid-liquid transition at the yielding point, characterized by yield stress and yield strain. It is well known in the literature that the elastic modulus and the yield stress of thixotropic materials increase with aging time. In the current work, we propose a discussion on the brittleness of a suspension of swollen bentonite in water, focusing mainly on the role of aging times on the yield strain and on the critical strain at the linear to nonlinear viscoelastic transition of the material. The yield strain was measured in creep and constant shear rate start-up experiments, whereas the linear to nonlinear viscoelastic transition was evaluated from Fourier transforms on transient data in oscillatory shear stress amplitude sweeps. We show that aging increases material brittleness since the yield strain decreases with the resting time. On the other hand, the linear to nonlinear viscoelastic transition strain is surprisingly unaffected by the aging process. Other thixotropic systems were also investigated: 8 and 10 wt. % suspensions of bentonite in water and a 2 wt. % suspension of Laponite® in tap water. These lead to similar observations, showing constant linear to nonlinear viscoelastic strains and decreasing yield strains over increasing aging times. These findings bring relevant information to the intricate open-discussion issue on how to describe the behavior of thixotropic materials below the yield stress.

Facile extrusion 3D printing of gelatine methacrylate/Laponite nanocomposite hydrogel with high concentration nanoclay for bone tissue regeneration

The extrusion 3D printing of hydrogels has evolved as a promising approach that can be applied for specific tissue repair. However, the printing process of hydrogel scaffolds with high shape fidelity is inseparable from the complex crosslinking strategy, which significantly increases the difficulty and complexity of printing. The aim of this study was to develop a printable hydrogel that can extrude at room temperature and print scaffolds with high shape fidelity without any auxiliary crosslinking during the printing process. To this end, a novel formulation consisting of a Laponite suspension with a high solid concentration and a gelatine methacrylate (GelMA) nanocomposite hydrogel was developed. A homogeneously dispersed high-concentration (up to 20% w/v) Laponite suspension was obtained by stirring at 0 °C. The addition of Laponite with high concentration improved the rheological properties, the degradation stability, and the mechanical strength of the hydrogel. The formulation of 15% (w/v) GelMA and 8% (w/v) Laponite nanocomposite hydrogel exhibited desirable printability and biocompatibility. The GelMA/Laponite hydrogels significantly promoted bone marrow mesenchymal stem cell (BMSC) proliferation and osteogenic differentiation. Both desirable printability under mild conditions and cyto-compatibility enable composite hydrogel a potential candidate as biomaterial inks to be applied for bone tissue regeneration.

Slip behavior during pressure driven flow of Laponite suspension

We investigate pressure driven pipe flow of Laponite suspension, as a model thixotropic fluid. The tendency of the suspension to age is controlled by addition of sodium chloride salt to vary the ionic strength. We use a syringe pump to prescribe the flow and observe that a steady state flow is obtained. Unusually, the steady state pressure drop required to maintain a constant flow rate decreases with an increase in the flow rate, in qualitative contrast to the expectation for Poiseuille flow. We demonstrate that experimental results obtained by varying the flow rate, salt concentration, and flow geometry (pipe diameter and length) can be collapsed onto a single universal curve that can be rationalized by invoking slip of the suspension at the tube walls. The Laponite suspension exhibits plug-like flow, yielding at the tube walls. Our results suggest that the slip length varies linearly with the flow rate and inversely with the tube diameter.

Study on the Rheological Behavior of a Model Clay Sediment

Clay sediments are the main component of seabed sediment. Interactions between the nano-sized, disk-shaped and charged clay particles are complicated, as they control the sediment’s rheology. In this study, we studied the rheological behavior of the clay sediment modeled by laponite and bentonite suspensions experimentally using a rotational rheometer. The yield stress decreased when water content increased. Meanwhile, the yield stress of the laponite suspension first increased and then decreased with increasing salinity. It is considered that the face-to-face repulsive electrostatic interaction between clay platelets dominated the yield behavior. A yield stress model was developed to describe the change of the yield stress with both the water content and the salinity. When the system started to flow, the viscosity decreased with increasing shear. A master curve of viscosity is was from the viscosity-stress curves at different water contents if the applied shear stress was normalized by the yield stress and the viscosity normalized by a characteristic viscosity. This study provides a preliminary understanding of the clay sediment rheology and its mechanism for the investigation on the flowing of the sediment systems with strong interparticle interaction.

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 suspensions 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 is 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.

Microscopic ergodicity breaking governs the emergence and evolution of elasticity in glass-forming nanoclay suspensions.

We report a study combining x-ray photon correlation spectroscopy (XPCS) with in situ rheology to investigate the microscopic dynamics and mechanical properties of aqueous suspensions of the synthetic hectorite clay Laponite, which is composed of charged, nanometer-scale, disk-shaped particles. The suspensions, with particle concentrations ranging from 3.25 to 3.75 wt%, evolve over time from a fluid to a soft glass that displays aging behavior. The XPCS measurements characterize the localization of the particles during the formation and aging of the soft-glass state. The fraction of localized particles, f_{0}, increases rapidly during the early formation stage and grows more slowly during subsequent aging, while the characteristic localization length r_{loc} steadily decreases. Despite the strongly varying rates of aging at different concentrations, both f_{0} and r_{loc} scale with the elastic shear modulus G^{'} in a manner independent of concentration. During the later aging stage, the scaling between r_{loc} and G^{'} agrees quantitatively with a prediction of naive mode coupling theory. Breakdown of agreement with the theory during the early formation stage indicates the prevalence of dynamic heterogeneity, suggesting the soft solid forms through precursors of dynamically localized clusters.

Osmotic-Pressure-Induced Nematic Ordering in Suspensions of Laponite and Carboxy Methyl Cellulose.

Laponite is a synthetic clay that is known to form gels in aqueous suspensions at low concentrations (0.01 g/cm3). Although it is expected to form lyotropic liquid crystals, such phases usually do not form, as a consequence of laponite's tendency to form gels at concentrations below the threshold for liquid crystal formation. Here we show that macroscopic, birefringent phases of laponite can be prepared through osmotic compression of a laponite solution by an aqueous solution of carboxy methyl cellulose (CMC). We present polarization imaging studies showing how the initially dilute, isotropic laponite phase shrinks while developing typical birefringence colors between crossed polarizers. Using the Michel-Lévy interference charts, we were able to extract the refractive index and orientation of the laponite nanodisks in the compressed region. Our observations allow us to propose a tentative state diagram, indicating the concentration regions for which we obtain optically anisotropic gels.

Couette flows of a thixotropic yield-stress material: Performance of a novel fluidity-based constitutive model

We present a theoretical and computational study of thixotropic yield-stress materials in cylindrical Couette flows using a novel fluidity-based constitutive model introduced by de Souza Mendes et al. [J. Nonnewtion. Fluid Mech. 261, 1–8 (2018)]. The model relies on measurable rheological properties to couple the equations of motion with an additional equation for the evolution of the material fluidity (i.e., the reciprocal of viscosity). The fluidity itself is used as a structure parameter to assess the material structuring state without the introduction of phenomenological functions or additional parameters. Our simulations parallel rheological tests with a stress-controlled rheometer and are carried out with the material properties obtained experimentally for the laponite suspension from which the model was originally developed. The results reveal that the processes of breakdown and buildup of the microstructure as well as the position of the yield surface in the flow essentially depend on the applied stress and on two material properties associated with distinct thixotropic time scales, namely, the avalanche time and the construction time. The model predictions also capture many features observed in the flow of yield-stress materials with thixotropy, such as the avalanche effect and transient shear banding. We also show that the steady-state flow is uniquely determined by the imposed stress and does not depend on the material initial structuring state. This contrasts with previous reports for nonthixotropic elastoviscoplastic materials, suggesting that nonunique steady flows of structured materials are probably associated with the transient evolution of elastic stresses from a given initial condition.

A Numerical Investigation of Different Behavioral Regimes of the Free-Falling Solid Objects in Laponite Suspension

In this paper, we have numerically examined models that are capable of describing free falling regimes of a rigid sphere in a thixotropic fluid as Laponite. By simultaneously solving the dynamical equations governing both sphere and fluid systems, different regimes referred to in the experimental methods, are obtained. Three common behavioral regimes are: i) quickly stopping object, ii) fall with decreasing velocity, and iii) falling with a constant velocity in a steady-state mode. The initial state of the fluids (which is a function of the aging time), the characteristic relaxation time of microstructure's building up under shear, the characteristic thickness of the yielded zone around the sphere, and critical yield stress value besides the diameter and density of the sphere are effective parameters that change the regime.

Rheological behavior for laponite and bentonite suspensions in shear flow

The viscometric behavior of laponite and bentonite suspensions at different concentrations in shear flow is studied. It is discovered that in the equilibrium state, a master curve of viscosity can be constructed when the applied shear stress is normalized by the respective suspension’s yield stress. The interparticle interaction controlling the yield behavior at the gel state also dominates the behavior of particles at the equilibrium flowing state. A constitutive framework is developed to describe the master curve of viscosity as a function of the shear stress normalized by the yield stress. Based on the proposed model, the effect of concentration on the viscosity of clay suspensions can be estimated via their yield stress.

Gel and glass transition in fragile colloidal clays

Dynamic Light Scattering (DLS) measurements were performed on colloidal suspensions of Laponite\textsuperscript{\textregistered} at different concentrations in the range $C_\text{w}= (1.5{\div}3.0)$%. The slowing down of the dynamics induced by aging was monitored by following the temporal evolution of autocorrelation functions at different concentrations towards the gel and glass transition. Exploiting analogies with supercooled liquids approaching their glass transitions, an Angell plot for the structural relaxation times was drawn. Finally, the fragility of Laponite\textsuperscript{\textregistered} suspensions at different concentrations, in different solvents, at two salt concentrations and with the addition of a polymer was reported and discussed.

Thermo-Responsive Nanocomposite Hydrogels Based on PEG-b-PLGA Diblock Copolymer and Laponite.

Poly(ethylene glycol)-b-poly(d,l-lactide-co-glycolide) (PEG-b-PLGA) diblock copolymers are widely known as polymeric surfactants for biomedical applications, and exhibit high solubility in water compared to PLGA-b-PEG-b-PLGA triblock copolymers known as gelation agents. In order to overcome the difficulties in the preparation of thermo-responsive hydrogels based on PLGA-b-PEG-b-PLGA due to the low solubility in water, the fabrication of thermo-responsive hydrogels based on PEG-b-PLGA with high solubility in water was attempted by adding laponite to the PEG-b-PLGA solution. In detail, PEG-b-PLGA with high solubility in water (i.e., high PEG/PLGA ratio) were synthesized. Then, the nanocomposite solution based on PEG-b-PLGA and laponite (laponite/PEG-b-PLGA nanocomposite) was fabricated by mixing the PEG-b-PLGA solutions and the laponite suspensions. By using the test tube inversion method and dynamic mechanical analysis (DMA), it was found that thermo-responsive hydrogels could be obtained by using PEG-b-PLGA, generally known as polymeric surfactants, and that the gelation temperature was around the physiological temperature and could be regulated by changing the solution composition. Furthermore, from the structural analysis by small angle neutron scattering (SANS), PEG-b-PLGA was confirmed to be on the surface of the laponite platelets, and the thermosensitive PEG-b-PLGA on the laponite surface could trigger the thermo-responsive connection of the preformed laponite network.

Nanoscale Laponite as a Potential Shale Inhibitor in Water-Based Drilling Fluid for Stabilization of Wellbore Stability and Mechanism Study.

Shale hydration is the main reason causing wellbore instability in oil and gas drilling operations. In this study, nanoscale laponite as a shale inhibitor was employed to stabilize wellbores. The inhibition property of laponite suspensions was evaluated by an immersion experiment, linear swelling measurement, and a shale recovery test. Then the shale inhibition mechanism was studied by using capillary suction time (CST) measurement, a thixotropy study, plugging performance evaluation, and related theoretical analysis. Evaluation experiment results showed that laponite had a better inhibition property than widely used inhibitors of potassium chloride (KCl) and poly(ester amine) (PA). The mechanism study revealed that integration of several factors strengthened the inhibition property of laponite suspensions. Laponite nanoparticles could plug interlayer spaces of clays by electrostatic interaction to reduce water invasion; the "house of cards" structure of laponite suspensions enables large CST values and low free water contents; the excellent thixotropy of a laponite nanofluid could allow a nanofilm to form in order to reduce water invasion into the formation; the nanoscale laponite particles could substantially reduce the shale permeability and form less porous surfaces. Furthermore, laponite could considerably decrease the filtrate volume of the drilling fluid, while KCl and PA had negative influences on the properties of the drilling fluid. This approach described herein might provide an avenue to inhibit shale hydration.

Self-Assembling Nanoclay Diffusion Gels for Bioactive Osteogenic Microenvironments.

Laponite nanoparticles have attracted attention in the tissue engineering field for their protein interactions, gel-forming properties, and, more recently, osteogenic bioactivity. Despite growing interest in the osteogenic properties of Laponite, the application of Laponite colloidal gels to host the osteogenic differentiation of responsive stem cell populations remains unexplored. Here, the potential to harness the gel-forming properties of Laponite to generate injectable bioactive microenvironments for osteogenesis is demonstrated. A diffusion/dialysis gelation method allows the rapid formation of stable transparent gels from injectable, thixotropic Laponite suspensions in physiological fluids. Upon contact with buffered saline or blood serum, nanoporous gel networks exhibiting, respectively, fivefold and tenfold increases in gel stiffness are formed due to the reorganization of nanoparticle interactions. Laponite diffusion gels are explored as osteogenic microenvironments for skeletal stem cell containing populations. Laponite films support cell adhesion, proliferation, and differentiation of human bone marrow stromal cells in 2D. Laponite gel encapsulation significantly enhances osteogenic protein expression compared with 3D pellet culture controls. In both 2D and 3D conditions, cell associated mineralization is strongly enhanced. This study demonstrates that Laponite diffusion gels offer considerable potential as biologically active and clinically relevant bone tissue engineering scaffolds.

Laponite Nanoparticle as a High Performance Rheological Modifier in Water-Based Drilling Fluids

In this paper, we demonstrated an artificial nanoparticles, Laponite, as a high performance rheological modifier in water-based drilling fluids. We made a comparison between Laponite nanoparticle and bentonite as rheological modifier in polyanionic cellulose (PAC) solution and weitghted water-based drilling fluids. In viscosity-shear rate test, both Laponite and bentonite could translate 0.5 wt.% PAC solution from Newton fluids to yield-pseudoplastic fluid. However, 1 wt.% Laponite was better in improving the shear-thinning behavior compared with 4 wt.% bentonite. In the stress-shear rate test, the results were fit with Bingham model with a high R2, and 1 wt.% Laponite/0.5 wt.% PAC suspension had a yield point of 5.19 Pa, which was higher than that of 4 wt.% bentonite/0.5 wt.% PAC suspension (3.13 Pa). Similarly, 1 wt.% Laponite/0.5 wt.% PAC suspension maintained a G’ of 12 Pa in the oscillation frequency sweep test, whereas G’ of 4%bentonite/0.5%PAC suspension was nearly 5 Pa. Particularly, 0.5 wt.% PAC /Laponite suspensions could maintain higher gel structure, yield point and better shear-thinning behaviors after 120°C hot rolling. The TEM image revealed that nanoscaled Laponite could form a “star network” with PAC in water, which explained the good rheological properties of PAC/LAP mixed suspensions. Besides, in the weighted drilling fluids, 1 wt.% Laponite could maintained a much higher gel strength compared with 4 wt.% bentonite.As the unique rheological properties, Laponite nanoparticles can greatly enhance abilities of water-based drilling fluids in circulating cuttings and making the borehole clean.