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.

Interfacial Tension of Phase-Separated Polydisperse Mixed Polymer Solutions.

Aqueous two-phase systems provide oil-free alternatives in the formulation of emulsions in food and other applications. Theoretical interpretation of measurements on such systems, however, is complicated by the high polydispersity of the polymers. Here, phase diagrams of demixing and interfacial tensions are determined for aqueous solutions of two large polymers present in a mass ratio of 1:1, dextran (70 kDa) and nongelling gelatin (100 kDa), with or without further addition of smaller dextran molecules (20 kDa). Both in experiments and in calculations from Scheutjens-Fleer self-consistent field lattice theory, we find that small polymers decrease the interfacial tension at equal tie-line length in the phase diagram. After identifying the partial contributions of all chemical components to the interfacial tension, we conclude that excess water at the interface is partially displaced by small polymer molecules. An interpretation in terms of the Gibbs adsorption equation provides an instructive way to describe effects of polydispersity on the interfacial tension of demixed polymer solutions.

Observation of solid-solid transitions in 3D crystals of colloidal superballs.

Self-organization in anisotropic colloidal suspensions leads to a fascinating range of crystal and liquid crystal phases induced by shape alone. Simulations predict the phase behaviour of a plethora of shapes while experimental realization often lags behind. Here, we present the experimental phase behaviour of superball particles with a shape in between that of a sphere and a cube. In particular, we observe the formation of a plastic crystal phase with translational order and orientational disorder, and the subsequent transformation into rhombohedral crystals. Moreover, we uncover that the phase behaviour is richer than predicted, as we find two distinct rhombohedral crystals with different stacking variants, namely hollow-site and bridge-site stacking. In addition, for slightly softer interactions we observe a solid-solid transition between the two. Our investigation brings us one step closer to ultimately controlling the experimental self-assembly of superballs into functional materials, such as photonic crystals.

Decreased Interfacial Tension of Demixed Aqueous Polymer Solutions due to Charge.

Electric charge at the water-water interface of demixed solutions of neutral polymer and polyelectrolyte decreases the already ultralow interfacial tension. This is demonstrated in experiments on aqueous mixtures of dextran (neutral) and nongelling fish gelatin (charged). Upon phase separation, electric charge and a potential difference develop spontaneously at the interface, decreasing the interfacial tension purely electrostatically in a way that can be accounted for quantitatively by Poisson-Boltzmann theory. Interfacial tension is a key property when it comes to manipulating the water-water interface, for instance to create novel water-in-water emulsions.

Smectite clay--inorganic nanoparticle mixed suspensions: phase behaviour and rheology.

Smectite clay minerals and their suspensions have long been of both great scientific and applications interest and continue to display a remarkable range of new and interesting behaviour. Recently there has been an increasing interest in the properties of mixed suspensions of such clays with nanoparticles of different size, shape and charge. This review aims to summarize the current status of research in this area focusing on phase behaviour and rheological properties. We will emphasize the rich range of data that has emerged for these systems and the challenges they present for future investigations. The review starts with a brief overview of the behaviour and current understanding of pure smectite clays and their suspensions. We then cover the work on smectite clay-inorganic nanoparticle mixed suspensions according to the shape and charge of the nanoparticles - spheres, rods and plates either positively or negatively charged. We conclude with a summary of the overarching trends that emerge from these studies and indicate where gaps in our understanding need further research for better understanding the underlying chemistry and physics.

Structure and rheology of mixed suspensions of montmorillonite and silica nanoparticles.

We present a study of the structure and rheology of mixed suspensions of montmorillonite clay platelets and Ludox TMA silica spheres at pH 5, 7, and 9. Using cryogenic transmission electron microscopy (cryo-TEM), we probe the changes in the structure of the montmorillonite suspensions induced by changing the pH and by adding silica particles. Using oscillatory and transient rheological measurements, we examine the changes in storage modulus and yield stress of the montmorillonite suspensions upon changing the pH and adding silica particles. Cryo-TEM images reveal that changes in pH have a significant effect on the structure of the suspensions, which can be related to the change in charge of the edges from positive at pH 5 to negative at higher pH. Furthermore, at pH 7, the cryo-TEM images show indications of a microphase separation between clay and silica particles. The addition of silica leads to lowering of the storage modulus and yield stress, which we connect to the structural changes of the suspension.

Effects of added silica nanoparticles on the nematic liquid crystal phase formation in beidellite suspensions.

In this article, we present a study of the liquid crystal phase behavior of mixed suspensions of the natural smectite clay mineral beidellite and nonadsorbing colloidal silica particles. While virtually all smectite clays dispersed in water form gels at very low concentrations, beidellite displays a first order isotropic-nematic phase transition before gel formation (J. Phys. Chem. B, 2009, 113, 15858-15869). The addition of silica nanospheres shifts the concentrations of the coexisting isotropic and nematic phases to slightly higher values while at the same time markedly accelerating the phase separation process. Furthermore, beidellite suspensions at volume fractions above the isotropic-nematic phase separation, trapped in a kinetically arrested gel state, liquefy on the addition of silica nanospheres and proceed to isotropic-nematic phase separation. Using small-angle X-ray scattering (SAXS), we probe the structural changes caused by the addition of the silica nanospheres, and we relate the modification of the phase transition kinetics to the change of the rheological properties.

Effects of added silica nanoparticles on hectorite gels.

We present a study on the macroscopic, microscopic, and rheological behavior of mixtures of natural hectorite clay and different types of anionic Ludox silica spheres. Adding silica spheres to the weak hectorite gels leads the collapse of the suspensions, while the strong gels remain space-filling, though their storage modulus and the yield stress values diminish. We discuss what kind of structural rearrangements are possibly responsible for the macroscopic and rheological changes in the clay/silica mixtures.

Lyotropic smectic B phase formed in suspensions of charged colloidal platelets.

Here, we present the first observation of a smectic B (Sm(B)) phase in a system of charged colloidal gibbsite platelets suspended in dimethyl sulfoxide (DMSO). The use of DMSO, a polar aprotic solvent, leads to a long range of the electrostatic Coulomb repulsion between platelets. We believe this to be responsible for the formation of the layered liquid crystalline phase consisting of hexagonally ordered particles, that is, the Sm(B) phase. We support our finding by high-resolution X-ray scattering experiments, which additionally indicate a high degree of ordering in the Sm(B) phase.

Structures and phase behavior in mixtures of charged colloidal spheres and platelets.

The experimental phase diagram for aqueous mixtures of charged gibbsite platelets and silica spheres is presented. The platelets are 95 nm in diameter, and the diameter ratio between the spheres and the platelets is 0.18. Here the spheres are acting as depletants in the mixtures perturbing the phase behavior of the pure platelet suspensions. An important finding is that a large isotropic/columnar coexistence region has been identified in the phase diagram, which appeared already at low concentrations of the platelets. Microradian X-ray diffraction measurements revealed the structure of the liquid crystalline phases and the orientational order of platelets. An interesting observation is that in the columnar phase the silica spheres are located between the columnar stacks. All samples were in equilibrium because sedimentation did not affect the system because of the relatively small size of the colloidal particles and the charges present at their surfaces.

Lyotropic hexagonal columnar liquid crystals of large colloidal gibbsite platelets.

We report the formation of hexagonal columnar liquid crystal phases in suspensions of large (570 nm diameter), sterically stabilized, colloidal gibbsite platelets in organic solvent. In thin cells these systems display strong iridescence originating from hexagonally arranged columns that are predominantly aligned perpendicularly to the cell walls. Small angle X-ray scattering and polarization microscopy indicate the presence of orientational fluctuations in the hexagonal columnar liquid crystal phase. The presence of decoupling of the average platelet orientation and the column axis as well as column undulations leading to a decrease of the effective column diameter are discussed. The fact that these phenomena are particularly pronounced in the vertical direction and are enhanced toward the bottom part of the system points to the role of gravitational compaction on the structure.

Sol-gel transitions and liquid crystal phase transitions in concentrated aqueous suspensions of colloidal gibbsite platelets.

In this paper, we present a comprehensive study of the sol-gel transitions and liquid crystal phase transitions in aqueous suspensions of positively charged colloidal gibbsite platelets at pH 4-5 over a wide range of particle concentrations (50-600 g/L) and salt concentrations (10(-4)-10(-1) M NaCl). A detailed sol-gel diagram was established by oscillatory rheological experiments. These demonstrate the presence of kinetically arrested states both at high and at low salt concentrations, enclosing a sol region. Birefringence and iridescence show that in the sol state nematic and hexagonal columnar liquid crystal phases are formed. The gel and liquid crystal structures are studied in further detail using small-angle X-ray scattering (SAXS) and cryo-focused ion beam/scanning electron microscopy (cryo-FIB-SEM). The gel formed at high salt concentration shows signatures of a sponge-like structure and does not display birefringence. In the sol region, by lowering the salt concentration and/or increasing the gibbsite concentration, the nematic phase gradually transforms from the discotic nematic (ND) into the columnar nematic (NC) with much stronger side-to-side interparticle correlations. Subsequently, this NC structure can be either transformed into the hexagonal columnar phase or arrested into a birefringent repulsive gel state with NC structure.

Shape and director field deformation of tactoids of plate-like colloids in a magnetic field.

We investigated by means of polarization microscopy the influence of a magnetic field on the shape and director field of nematic droplets in dispersions of plate-like colloidal particles. To interpret the experimental observations, we put forward a simple theory in which we presume strong anchoring and a sphero-cylindrical droplet shape. This model allows us to extract values for the interfacial tension and the splay elastic constant from the experimental data.

Formation of nematic liquid crystals of sterically stabilized layered double hydroxide platelets.

Colloidal platelets of hydrotalcite, a layered double hydroxide, have been prepared by coprecipitation at pH 11-12 of magnesium nitrate and aluminum nitrate at two different magnesium to aluminum ratios. Changing the temperature and ionic strength during hydrothermal treatment, the platelets were tailored to different sizes and aspect ratios. Amino-modified polyisobutylene molecules were grafted onto the platelets following a convenient new route involving freeze-drying. Organic dispersions in toluene were prepared of the particles with the largest size and highest aspect ratio. The colloidal dispersions prepared in this way showed isotropic-nematic phase transitions above a limiting concentration in a matter of days. The number density at the transition and the width of the biphasic region were determined and compared to theory. The orientation of the platelets in nematic droplets (tactoids) and at the isotropic-nematic interface were analyzed by polarization microscopy. It was observed that sedimentation induces a nematic layer in samples that are below the limiting concentration for isotropic-nematic phase separation. No nematic phase was observed in the initial aqueous suspensions of the ungrafted particles.

Rheology modification in mixed shape colloidal dispersions. Part II: mixtures.

We report the results of a comprehensive study of the rheological properties of a series of mixed colloid systems where the shape of one of the components has been varied systematically. Specifically we have measured the oscillatory, transient (creep) and continuous steady shear flow behaviour of a 2.5 wt% dispersion in water of a well-characterised hectorite clay modified by the addition of a series of aluminasol colloidal particles whose shape varies systematically from rod (boehmite) to platelet (gibbsite) to sphere (alumina-coated silica), all having essentially the same smallest dimension, which is similar to that of the hectorite. The particle characterisation and rheological properties of the pure components have recently been reported in Part I of this series (Soft Matter, 2007, 3, 1145). The mixtures show the same general behaviour as the pure systems, displaying a complex 'yield space' transition from an elastoviscous gel at low applied stresses to a viscous, weakly elastic, shear-thinning liquid at high stresses. The unifying theme of this work is that the addition of 0.25 wt% of the minor component in all cases results in dramatic enhancements to the dispersion rheological properties. At the same time the magnitude of this effect depends on the shape of the particles. Shear moduli, low stress viscosities and effective yield stresses all increase in the additive order rods < platelets < spheres, with enhancements for the latter being up to a factor of 500 and typically 20. At the same time the critical failure strains for the gels decreased in the same order - the strongest gels are also the most fragile in this sense. The physicochemical factors underlying this behaviour are discussed and a simple qualitative model described. While no complete explanation or model can be proposed at this stage, the study provides a quantitative model-system baseline for mixed colloidal dispersions already used for industrial applications (e.g. oilwell-drilling fluids) and suggests ways in which such fluids may be optimised and controlled.

Fast formation of opal-like columnar colloidal crystals.

We demonstrate that highly polydisperse colloidal gibbsite platelets easily form an opal-like columnar crystal with striking iridescent Bragg reflections. The formation process can be accelerated by orders of magnitude under a centrifugation force of 900 g without arresting the system in a disordered glassy phase. Using transmission electron microscopy and small-angle X-ray scattering techniques, we find that the forced sedimentation is accompanied by particle size fractionation, leading to inversion of the iridescent colors. The relatively easy self-organization of the polydisperse colloidal particles into opal-like crystals may be explained on the basis of the observed particle fractionation and possibly also on hexatic-like ordering.

Rheology modification in mixed shape colloidal dispersions. Part I: pure components.

The flow behaviour and rheology of colloidal dispersions are of considerable interest in many applications, for example colloidal clay particles find applications in oilfield and construction-drilling fluids. The rheological properties of such fluids can be enhanced significantly by adding colloidal particles of different size and shape. To gain insight into the mechanism of this phenomenon, we have studied model mineral-colloid systems whose shape changes systematically from a plate-like aluminasol (gibbsite), through a lath-like smectite clay (hectorite), to a rod-like aluminasol (boehmite).The paper presents the results of a systematic and comprehensive multi-technique study (oscillatory, transient and steady shear) of the rheology of dispersions of these model systems. This gives a detailed account of the 'yield space' that characterises the complex transition of these soft materials from elastoviscous gels to viscoelastic liquids, and of the effect of particle size and shape on this behaviour. The observed phenomena are underpinned by two competing flow-mediated microstructural rearrangements that have significantly different timescales. A physical model invoking flow-mediated building and disruption of fluid structure is described to rationalise the observed behaviour. The study also forms the baseline to a companion study (part II), which investigates the rheological behaviour of mixed anisometric colloid systems based on these pure components.

Suppression of thermally excited capillary waves by shear flow.

We investigate the thermal fluctuations of the colloidal gas-liquid interface subjected to a shear flow parallel to the interface. Strikingly, we find that the shear strongly suppresses capillary waves, making the interface smoother. This phenomenon can be described by introducing an effective interfacial tension that increases with the shear rate. The increase of sigma(eff) is a direct consequence of the loss of interfacial entropy caused by the flow, which affects especially the slow fluctuations. This demonstrates that the interfacial tension of fluids results from an intrinsic as well as a fluctuation contribution.

Devitrification of colloidal glasses in real space.

Confocal scanning laser microscopy has been used to quantitatively analyze the structure and dynamics of concentrated suspensions of spherical colloids in which the magnitude of the short-range attractive potential is increased by adding nonadsorbing polymers. These systems undergo a reentrant glass transition upon increasing polymer concentration. We find that melting of the glass is accompanied by significant changes in the displacement distribution and its moments. However, no significant variations have been detected in the shapes of the displacement distributions. Moreover, structural correlation functions and the magnitude of local density fluctuations do not vary significantly between the glass states and the fluid. Considering our experimental setup, these observations imply that local density fluctuations cannot be larger than a few percent of the average density.