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.

We describe the synthesis of hybrid magnetic ellipsoidal nanoparticles that consist of a mixture of two different iron oxide phases, hematite (α-Fe 2 O 3 ) and maghemite (γ-Fe 2 O 3 ), and characterize their magnetic field-driven self-assembly. We demonstrate that the relative amount of the two phases can be adjusted in a continuous way by varying the reaction time during the synthesis, leading to strongly varying magnetic properties of the particles. Not only does the saturation magnetization increase dramatically as the composition of the spindles changes from hematite to maghemite, but also the direction of the induced magnetic moment changes from being parallel to the short axis of the spindle to being perpendicular to it.The magnetic dipolar interaction between the particles can be further tuned by adding a screening silica shell. Small-angle X-ray scattering (SAXS) experiments reveal that at high magnetic field, magnetic dipole-dipole interaction forces the silica coated particles to self-assemble into a distorted hexagonal crystal structure at high maghemite content. However, in the case of uncoated maghemite particles, the crystal structure is not very prominent. We interpret this as a consequence of the strong dipolar interaction between uncoated spindles that then become arrested during field-induced self-assembly into a structure riddled with defects.

Manipulation of the self-assembly of magnetic colloidal particles by an externally applied magnetic field paves a way toward developing novel stimuli responsive photonic structures. Using microradian X-ray scattering technique we have investigated the different crystal structures exhibited by self-assembly of core-shell magnetite/silica nanoparticles. An external magnetic field was employed to tune the colloidal crystallization. We find that the equilibrium structure in absence of the field is random hexagonal close-packed (RHCP) one. External field drives the self-assembly toward a body-centered tetragonal (BCT) structure. Our findings are in good agreement with simulation results on the assembly of these particles.

Anisotropic dynamics on the colloidal length scale is ubiquitous in nature. Of particular interest is the dynamics of systems approaching a kinetically arrested state. The failure of classical techniques for investigating the dynamics of highly turbid suspensions has contributed toward the limited experimental information available up until now. Exploiting the recent developments in the technique of differential dynamic microscopy (DDM), we report the first experimental study of the anisotropic collective dynamics of colloidal ellipsoids with a magnetic hematite core over a wide concentration range approaching kinetic arrest. In addition, we have investigated the effect of an external magnetic field on the resulting anisotropic collective diffusion. We combine DDM with small-angle x-ray scattering and rheological measurements to locate the glass transition and to relate the collective short- and long-time diffusion coefficients to the structural correlations and the evolution of the zero shear viscosity as the system approaches an arrested state.

The influence of an applied magnetic field on the collective dynamics of novel anisotropic colloidal particles whose shape resembles peanuts is reported. Being made up of hematite cores and silica shells, these micrometer-sized particles align in a direction perpendicular to the applied external magnetic field, and assemble into chains along the field direction. The anisotropic dynamics of these particles is investigated using multispeckle ultrasmall-angle X-ray photon correlation spectroscopy (USA-XPCS). The results indicate that along the direction of the magnetic field, the particle dynamics strongly depends on the length scale probed. Here, the relaxation of the intermediate scattering function follows a compressed exponential behavior at large distances, while it appears diffusive at distances comparable or smaller than the particle size. Perpendicular to the applied field (and along the direction of gravity), the experimental data can be quantitatively reproduced by a combination of an advective term originating from sedimentation and a purely diffusive one that describes the thermal diffusion of the assembled chains and individual particles.

We demonstrate a unique shear-induced crystallization phenomenon above the equilibrium freezing temperature ðT o K Þ in weakly swollen isotropic ðL i Þ and lamellar ðL α Þ mesophases with bilayers formed in a cationic-anionic mixed surfactant system. Synchrotron rheological X-ray diffraction study reveals the crystallization transition to be reversible under shear (i.e., on stopping the shear, the nonequilibrium crystalline phase L c melts back to the equilibrium mesophase). This is different from the shear-driven crystallization below T o K , which is irreversible. Rheological optical observations show that the growth of the crystalline phase occurs through a preordering of the L i phase to an L α phase induced by shear flow, before the nucleation of the L c phase. Shear diagram of the L i phase constructed in the parameter space of shear rate ð_ γÞ vs. temperature exhibits L i → L c and L i → L α transitions above the equilibrium crystallization temperature ðT o K Þ, in addition to the irreversible shear-driven nucleation of L c in the L i phase below T o K . In addition to revealing a unique class of nonequilibrium phase transition, the present study urges a unique approach toward understanding shear-induced phenomena in concentrated mesophases of mixed amphiphilic systems.shear-induced phase separation | strongly binding counterions | coagels S hear is known to assist crystallization below the equilibrium freezing temperature in complex fluids like colloidal glasses (1, 2), dense granular suspensions (3), polymer melts (4, 5), micellar solutions of block copolymers (6), and multicomponent surfactant systems (7,8). Shear-driven crystallization is equally relevant for simple fluids like bulk metallic glasses (9), molecular liquids (10), and atomic systems (11). The general understanding is that shear lowers the energy barrier for nucleation and accelerates the growth of a stable crystalline phase from a metastable, amorphous/ isotropic solution at Peclet number Pe = σa 3 kBT > 1, where σ is the shear stress, a is the characteristic length scale, and k B T is the thermal energy (12). The crystalline phase primarily induced by the effect of flow on the internal structure and ordering of the constituents does not revert to the starting fluid state when the imposed shear is removed, indicating that the phenomenon is not a dynamic phase transition. In the present study, we report a unique phenomenon, where under steady shear, crystallization occurs above the equilibrium crystallization temperature ðT o K Þ in an isotropic mesophase ðL i Þ consisting of bilayers formed in a lyotropic surfactant system. Notably, above T o K , when the imposed shear is removed, the crystalline phase melts back to the starting L i phase.The studies were carried out in a cationic-anionic mixed surfactant system formed by SDS and the strong binding counter-ion paratoluene hydrochloride (PTHC) in water. At equilibrium, the organic counter-ion PTHC has the tendency to remain at the micelle-water interface, decreasing the spontaneous curvat...

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We present a phenomenological theory of phase transitions in achiral lipid membranes in terms of two coupled order parameters -a scalar order parameter describing lipid chain melting, and a vector order parameter describing the tilt of the hydrocarbon chains below the chain-melting transition. Existing theoretical models fail to account for all the observed features of the phase diagram, in particular the detailed microstructure of the asymmetric ripple phase lying between the fluid and the tilted gel phase. In contrast, our two-component theory reproduces all the salient structural features of the ripple phase, providing a unified description of the phase diagram and microstructure. PACS numbers: 87.16.D-,61.30.DkPhospholipids self-assemble in water to form a rich variety of spatially modulated phases [1]. The simplest of these is the 1-dimensionally modulated fluid lamellar phase (L α ) consisting of periodic stacks of lipid bilayer membranes separated by water, where the hydrocarbon chains are floppy with liquid-like in-plane order. Changing the temperature or water content induces a sequence of symmetry breaking transitions characterized by unique microstructures.On reducing the temperature below the chain melting (main) transition (T m ), the L α phase of phosphatidylcholines (PCs) transforms to a gel phase (L β ′ ), characterized by fully-stretched all − trans chains which are tilted with respect to the bilayer normal [2][3][4]. In addition, an asymmetric ripple phase (P β ′ ) is found to occur in between the L α and L β ′ phases in many PCs at high water content [1,2,5].Extensive studies using a variety of experimental techniques [1,[6][7][8][9][10][11][12][13][14][15][16][17][18], reveal that the P β ′ phase is characterized by a periodic saw-tooth height modulation of the bilayers having an amplitude of ∼ 1 nm and a wavelength of ∼ 15 nm, and a bilayer thickness that is different in the two arms of the ripple ( fig. 1) [9,10]. As a result, the rippled bilayers lack a mirror plane normal to the rippling direction. While in principle, this discrete symmetry breaking can arise from an asymmetry in either shape (unequal lengths of the two arms) or bilayer thickness (unequal bilayer thickness in the two arms), in practice these asymmetries seem to appear simultaneously.At first it was believed that the origins of the asymmetric ripple lay in the chirality of lipid molecules [20]. However, subsequent experiments using racemic mixtures showed this was not the case [8,15]. More recently, all-atom molecular dynamics simulations of lipid bilayers have observed that the degree of chain ordering is different in the two arms of the ripple [21]. The occurrence of the ripple phase only in those lipids that exhibit a L β ′ phase at lower temperatures [22], and in isolated bilayers [23], suggests an intimate connection between chain tilt and the ability of the bilayers to form ripples.Several theoretical models have been proposed to describe the sequence of phase transitions in such lipid bilayers and the microstructure ...