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Anisotropic colloidal particles exhibit complex dynamics which play a crucial role in their functionality, transport and phase behaviour. In this work, we investigate the two-dimensional diffusion of smoothly curved colloidal rods -- also known as colloidal bananas -- as a function of their opening angle, {\alpha}. We measure the translational and rotational diffusion coefficients of the particles with opening angles ranging from 0{\deg} (straight rods) to nearly 360{\deg}(closed rings). In particular, we find that the anisotropic diffusion of the particles varies non-monotonically with their opening angle and that the axis of fastest diffusion switches from the long to the short axis of the particles when {\alpha}>180{\deg}. We also find that the rotational diffusion coefficient of nearly closed rings is approximately an order of magnitude higher than that of straight rods of the same length. Finally, we show that the experimental results are consistent with Slender Body Theory, indicating that the dynamical behavior of the particles arises primarily from their local drag anisotropy. These results highlight the impact of curvature on the Brownian Motion of elongated colloidal particles, which must be taken into account when seeking to understand the behaviour of curved colloidal particles., Comment: 5 pages (including references) and 4 figures

We optimize and characterize the preparation of 3-trimethoxysilyl propylmethacrylate (TPM) colloidal suspensions for three-dimensional confocal microscopy. We revisit a simple synthesis of TPM microspheres by nucleation of droplets from pre-hydrolyzed TPM oil in a 'zero-flow' regime, and demonstrate how precise and reproducible control of particle size may be achieved via single-step nucleation with a focus on how the reagents are mixed. We also revamp the conventional dyeing method for TPM particles to achieve uniform transfer of a fluorophore to the organosilica droplets, improving particle identification. Finally, we illustrate how a ternary mixture of tetralin, trichloroethylene and tetrachloroethylene may be used as a suspension medium which matches the refractive index of these particles while allowing independent control of the density mismatch between particle and solvent., Comment: 27 pages, 6 Figures

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We study the crystallization of colloidal dispersions under capillary-action-induced shear as the dispersion is drawn into flat walled capillaries. Using confocal microscopy and small angle x-ray scattering, we find that the shear near the capillary walls influences the crystallization to result in large random hexagonal close-packed (RHCP) crystals with long-range orientational order over tens of thousands of colloidal particles. We investigate the crystallization mechanism and find partial crystallization under shear, initiating with hexagonal planes at the capillary walls, where shear is highest, followed by epitaxial crystal growth from these hexagonal layers after the shear is stopped. We then characterize the three-dimensional crystal structure finding that the shear-induced crystallization leads to larger particle separations parallel to the shear and vorticity directions as compared to the equilibrium RHCP structure. Confocal microscopy reveals that competing shear directions, where the capillary walls meet at a corner, create differently oriented hexagonal planes of particles. The single-orientation RHCP colloidal crystals remain stable after formation and are produced without the need of complex shear cell arrangements.

Unlike crystals, glasses age or devitrify over time, reflecting their non-equilibrium nature. This lack of stability is a serious issue in many industrial applications. Here, we show by numerical simulations that the devitrification of quasi-hard-sphere glasses is prevented by suppressing volume fraction inhomogeneities. A monodisperse glass known to devitrify with `avalanche'-like intermittent dynamics is subjected to small iterative adjustments to particle sizes to make the local volume fractions spatially uniform. We find that this entirely prevents structural relaxation and devitrification over aging time scales, even in the presence of crystallites. There is a dramatic homogenization in the number of load-bearing nearest neighbors each particle has, indicating that ultra-stable glasses may be formed via `mechanical homogenization'. Our finding provides a physical principle for glass stabilization and opens a novel route to the formation of mechanically stabilized glasses., 6 pages, 4 figures, 1 ancillary video file, 1 supplementary PDF

Surface roughness plays an important role in determining the mechanical properties, wettability, and self-assembly in colloidal systems. In this work, we develop a simple and fast method to produce rough colloidal SU-8 rods, bananas, and spheres, via the nanoprecipitation of SU-8 in water. During this process, SU-8 nanospheres are absorbed onto the surface of the colloidal SU-8 particles and then cross-linked using UV-light. The size of the spherical asperities and the asperity density are controlled by the concentration of SU-8 used during the nanoprecipitation reaction. Fluorescent labeling of the rough SU-8 colloidal particles allows for their confocal imaging, which demonstrates their stability at high packing fractions. With these newly developed rough particles, we provide a colloidal model system that allows for studies addressing the impact of surface roughness on materials composed of anisotropic particles.

Photo-catalytically active crystalline TiO2 has attracted special attention due to its relevance for renewable energy and is typically obtained by the calcination of amorphous TiO2. However, stabilising hollow colloidal TiO2 particles against aggregation during calcination without compromising their photocatalytic activity poses two conflicting demands: to be stable their surface needs to be coated, while efficient photocatalysis requires an exposed TiO2 surface. Here, this incompatibility is resolved by partially coating TiO2 shells with evenly distributed 3-trimethoxysilyl propyl methacrylate (TPM) lobes. These lobes act both as steric barriers and surface charge enhancers that efficiently stabilise the TiO2 shells against aggregation during calcination. The morphology of the TPM lobes and their coverage, and the associated particle stability during the calcination-induced TiO2 crystallization, can be controlled by the pH and the contact angle between TPM and TiO2. The crystal structure and the grain size of the coated TiO2 shells are controlled by varying the calcination temperature, which allows tuning their photocatalytic activity. Finally, the durable photocatalytic activity over many usage cycles of the coated TiO2 compared to uncoated shells is demonstrated in a simple way by measuring the photo-degradation of a fluorescent dye. Our approach offers a general strategy for stabilising colloidal materials, without compromising access to their active surfaces.

We characterise the local mechanical properties of two-dimensional colloidal crystals with hexagonal symmetry assembled at the flat interface between oil and water. Our experiments elucidate the conditions under which the material behaves isotropically, as opposed to those where the microstructure plays a major role. Brownian fluctuations are used to extract the stiffness of the lattice under the continuum approximation, whereas at larger displacements, obtained by optically driving one particle through the structure, the mechanical resistance of the lattice depends on both the area fraction and the direction of the applied force. Remarkably, the minimum resistance does not necessarily correspond to a probe being driven between neighbours, i.e. at 30° with respect to the crystal axes.

Photo-catalytically active crystalline TiO2 has attracted special attention due to its relevance for renewable energy and is typically obtained by the calcination of amorphous TiO2. However, stabilising hollow colloidal TiO2 particles against aggregation during calcination without compromising their photocatalytic activity poses two conflicting demands: to be stable their surface needs to be coated, while efficient photocatalysis requires an exposed TiO2 surface. Here, this incompatibility is resolved by partially coating TiO2 shells with evenly distributed 3-trimethoxysilyl propyl methacrylate (TPM) lobes. These lobes act both as steric barriers and surface charge enhancers that efficiently stabilise the TiO2 shells against aggregation during calcination. The morphology of the TPM lobes and their coverage, and the associated particle stability during the calcination-induced TiO2 crystallization, can be controlled by the pH and the contact angle between TPM and TiO2. The crystal structure and the grain size of the coated TiO2 shells are controlled by varying the calcination temperature, which allows tuning their photocatalytic activity. Finally, the durable photocatalytic activity over many usage cycles of the coated TiO2 compared to uncoated shells is demonstrated in a simple way by measuring the photo-degradation of a fluorescent dye. Our approach offers a general strategy for stabilising colloidal materials, without compromising access to their active surfaces.

The rotational Brownian motion of colloidal spheres in dense suspensions reflects local hydrodynamics and contact forces, which are both key to nonlinear rheological phenomena such as shear-thickening and jamming, and transport in crowded environments, including intracellular migration and blood flow. To fully elucidate the role of rotational dynamics experimentally, it is crucial to measure the translational and rotational motion of all spheres simultaneously. Here, we directly access hydrodynamic and frictional coupling in colloidal suspensions up to arbitrarily high volume fractions using compositionally uniform colloidal spheres with an off-center, fully embedded core. We reveal interparticle hydrodynamic rotation-rotation coupling in charged colloidal crystals. We also find that higher local crystallinity in denser hard-sphere crystalline sediments enhances rotational diffusivity and that nearly arrested particles exhibit a stick-slip rotational motion due to frictional coupling. Our findings shed new light on the largely unexplored, local rotational dynamics of spherical particles in dense particulate materials.

The properties of a wide range of two-dimensional network materials are investigated by developing a generalized network theory. The methods developed are shown to be applicable to a wide range of systems generated from both computation and experiment; incorporating atomistic materials, foams, fullerenes, colloidal monolayers, and geopolitical regions. The ring structure in physical networks is described in terms of the node degree distribution and the assortativity. These quantities are linked to previous empirical measures such as Lema\^{\i}tre's law and the Aboav-Weaire law. The effect on these network properties is explored by systematically changing the coordination environments, topologies, and underlying potential model of the physical system.

The effect of hydrodynamic interactions (HI) on the long-time self-diffusion in quasi-two-dimensional fluids of paramagnetic colloidal particles is investigated using a combination of experiments and Brownian dynamics (BD) simulations. In the BD simulations, the direct interactions (DI) between the particles consist of a short-ranged repulsive part and a long-ranged part that is proportional to 1/r^{3}, with r the interparticle distance. By studying the equation of state, the simulations allow for the identification of the regime where the properties of the fluid are fully controlled by the long-ranged interactions, and the thermodynamic state solely depends on the dimensionless interaction strength Γ. In this regime, the radial distribution functions from the simulations are in quantitative agreement with those from the experiments for different fluid area fractions. This agreement confirms that the DI in the experiments and simulations are identical, which thus allows us to isolate the role of HI, as these are not taken into account in the BD simulations. Experiment and simulation fall onto a master curve with respect to the Γ dependence of D_{L}^{★}=D_{L}/(D_{0}Γ^{1/2}), with D_{0} the self-diffusion coefficient at infinite dilution and D_{L} the long-time self-diffusion coefficient. Our results thus show that, although HI affect the short-time self-diffusion, for a quasi-two-dimensional system with 1/r^{3} long-ranged DI, the reduced quantity D_{L}^{★} is effectively not affected by HI. Interestingly, this is in agreement with prior work on quasi-two-dimensional colloidal hard spheres.

The formation and kinetics of grain boundaries are closely related to the topological constraints imposed on their complex dislocation structure. Loop-shaped grain boundaries are unique structures to establish such a link because their overall topological "charge" is zero due to their null net Burgers vector. Here, we observe that a local rotational deformation of a 2D colloidal crystal with an optical vortex results in a grain boundary loop only if the product of its radius and misorientation exceeds a critical value. Above this value, the deformation is plastic and the grain boundary loop spontaneously shrinks at a rate that solely depends on this product, while otherwise, the deformation is elastically restored. We show that this elastic-to-plastic crossover is a direct consequence of the unique dislocation structure of grain boundary loops. At the critical value, the loop is structurally equivalent to the so-called "flower defect" and the shrinkage rate diverges. Our results thus reveal a general limit on the formation of grain boundary loops in 2D crystals and elucidate the central role of defects in both the onset of plasticity and the kinetics of grain boundaries.

We study the effects of concentration, surface area and surface chemistry of fractal fumed silica aggregates on a model fat-structured food system. We use oscillatory stress sweep rheology to determine the storage modulus, the length of the linear viscoelastic region and the rate of network breakdown after the linear region. Differential scanning calorimetry shows that silica is not acting as a seed for nucleation and that the melting profiles for samples with silica are not significantly different. We interpret these results in terms of hydrogen bonding between the silica aggregates and its role in strengthening the fat crystal networks.

We report a straightforward, model-free approach for measuring pair potentials from particle-coordinate data, based on enforcing consistency between the pair distribution function measured separately by the distance-histogram and test-particle insertion routes. We demonstrate the method's accuracy and versatility in simulations of simple fluids, before applying it to an experimental system composed of superparamagnetic colloidal particles. The method will enable experimental investigations into many-body interactions and allow for effective coarse-graining of interactions from simulations., Comment: 8 pages, 3 figures including supplemental material

We discuss the various mechanisms involved in the spontaneous shrinkage of circular grain boundaries in two-dimensional colloidal crystals. We provide experimental evidence that these grain boundary loops shrink owing to three intermittent mechanisms proposed for atomic materials, namely purely curvature-driven migration, coupled grain boundary migration, and grain boundary sliding. Throughout shrinkage, the product of the radius and misorientation of the grain boundary loop remains higher than a fundamental limit resulting from the specific dislocation structure of grain boundary loops, except for the very last stage where the loop character is lost. Despite its complexity, this process can be effectively described by a single kinetic coefficient, allowing for a simplified description of grain boundary loop kinetics.

We describe the synthesis and application of 3-(trimethoxysilyl)propyl methacrylate (TPM) particles as a colloidal model system for three-dimensional (3D) confocal scanning laser microscopy. The effect of the initial TPM concentration on the growth and polydispersity of the particles and a recently developed solvent transfer method to disperse particles in a refractive index and density-matching solvent mixture are reviewed and discussed. To fully characterize the system as a colloidal model, we measure the pair potential between the TPM particles directly using optical tweezers. Finally, we use 3D confocal microscopy to image a sedimentation-diffusion equilibrium of TPM particles to characterize the phase behavior and particle dynamics through successful detection and tracking of all particles in the field of view.

A colloidal particle is driven across a temporally oscillating one-dimensional optical potential energy landscape and its particle motion is analysed. Different modes of dynamic mode locking are observed and are confirmed with the use of phase portraits. The effect of the oscillation frequency on the mode locked step width is addressed and the results are discussed in light of a high-frequency theory and compared to simulations. Furthermore, the influence of the coupling between the particle and the optical landscape on mode locking is probed by increasing the maximum depth of the optical landscape. Stronger coupling is seen to increase the width of mode locked steps. Finally, transport across the temporally oscillating landscape is studied by measuring the effective diffusion coefficient of a mobile particle, which is seen to be highly sensitive to the driving velocity and mode locking.

The bulk synthesis of fluorescent colloidal SU‐8 polymer rods with tunable dimensions is described. The colloidal SU‐8 rods are prepared by shearing an emulsion of SU‐8 polymer droplets and then exposing the resulting non‐Brownian rods to ultrasonic waves, which breaks them into colloidal rods with typical lengths of 3.5–10 µm and diameters of 0.4–1 µm. The rods are stable in both aqueous and apolar solvents, and by varying the composition of apolar solvent mixtures both the difference in refractive index and mass density between particles and solvent can be independently controlled. Consequently, these colloidal SU‐8 rods can be used in both 3D confocal microscopy and optical trapping experiments while carefully tuning the effect of gravity. This is demonstrated by using confocal microscopy to image the liquid crystalline phases and the isotropic–nematic interface formed by the colloidal SU‐8 rods and by optically trapping single rods in water. Finally, the simultaneous confocal imaging and optical manipulation of multiple SU‐8 rods in the isotropic phase is shown.

We study the static and dynamic behaviour of colloidal rods in an optical potential energy landscape. We explore the stable states of a colloidal rod in a single optical trap close to a flat wall. Here, two metastable states are observed, horizontal and vertical, both of which experience a parabolic potential energy landscape. Next we place a colloidal rod into a one-dimensional sinusoidal optical potential energy landscape and introduce a constant driving velocity. When driven below the critical velocity, the particle is confined to a single potential energy minimum of the optical landscape and the equilibrium position of a particle is investigated. The equilibrium position of a rod is found to vary substantially from that of a sphere, due to the drag coefficient of a rod being highly dependent on its proximity to an optical trap. The driving velocity is increased to enable the particle to traverse the periodic landscape and above the critical velocity, the average particle velocity increases as the square root of the driving velocity. When introducing oscillations to the driving velocity we observe dynamic mode locking and characterise the nature of synchronised motion of the rod-like particles.

Colloidal particles with asymmetric catalytic activities are emerging micro/nanomotors that harvest chemical energy for propulsion in fluids. It is of general interest to produce such particles with high performance, in large quantity and at low cost. In this paper, we present a facile bulk method to synthesize silver-head colloidal silica rods. These particles self-propel towards their active sites by reacting with hydrogen peroxide, and the velocity is tuned via the fuel concentration. We show that these motors are highly efficient; compared to the currently available chemical-phoretic micro/nanomotors they show similar performance of self-propulsion at fuel concentrations that are two orders of magnitude smaller.

We apply Henderson's method for measuring the cavity distribution function y(r) [J. Henderson, Mol. Phys. 48, 389 (1983)] to obtain the pair distribution function at contact, g(σ+). In contrast to the conventional distance-histogram method, no approximate extrapolation to contact is required. The resulting equation of state from experiments and simulations of hard disks agrees well with the scaled particle theory prediction up to high fluid packing fractions. We also provide the first experimental measurement of y(r) inside the hard core, which will allow for a more complete comparison with theory. The method's flexibility is further illustrated by measuring the partial pair distribution functions of binary hard-disk mixtures in simulation. The equation for the contact values can be used to derive familiar results from statistical geometry.

Hard disks are one of the simplest interacting many-body model system in two dimensions (2D). Here, we present a comprehensive set of measurements of the static structure factors for quasi-2D monodisperse fluids and two different binary colloidal hard sphere mixtures: a small size ratio (SSR) system with a negligibly small negative non-additivity and a large size ratio system with a significantly larger non-additivity. We compare the experimental results for the monodisperse and SSR systems to those calculated using density functional theory (DFT) for additive mixtures. Furthermore, we determine the zero-wavevector limits of the static structure factors for the monodisperse and binary hard sphere fluids directly from an analysis of number and concentration fluctuations. For the monodisperse case, this leads to the isothermal compressibility, which agrees very well with DFT, and is consistent with the scaled particle theory equation of state for hard disks. For the binary fluids, the partial static structure factors are used to calculate the Bhatia–Thornton structure factors, and we find qualitative agreement with DFT for the SSR mixture. Finally, the zero-wavevector limits of the Bhatia–Thornton structure factors are determined and directly related to the thermodynamic factor, the dilatation factor and the isothermal compressibility.

© 2018, © 2018 Informa UK Limited, trading as Taylor & Francis Group. We confine a colloidal liquid crystal between parallel plates separated down to several times the rod length. By connecting the system to a reservoir we effectively create a grand canonical system, in which the liquid crystal displays an isotropic phase in the reservoir, but upon strong confinement becomes nematic between the parallel plates. This capillary nematisation transition can be followed down to the single particle level by means of laser scanning confocal microscopy. We compare the experimental findings to density functional theories (DFTs), within the Zwanzig model as well as a more advanced DFT, in which the effect of rod flexibility is taken into account. ispartof: Molecular Physics vol:116 issue:21-22 pages:2864-2871 status: published

Using dynamical density functional theory (DDFT), we theoretically study Brownian self-diffusion and structural relaxation of hard disks and compare to experimental results on quasi two-dimensional colloidal hard spheres. To this end, we calculate the self-van Hove correlation function and distinct van Hove correlation function by extending a recently proposed DDFT-approach for three-dimensional systems to two dimensions. We find that the theoretical results for both self-part and distinct part of the van Hove function are in very good quantitative agreement with the experiments up to relatively high fluid packing fractions of roughly 0.60. However, at even higher densities, deviations between the experiment and the theoretical approach become clearly visible. Upon increasing packing fraction, in experiments, the short-time self-diffusive behavior is strongly affected by hydrodynamic effects and leads to a significant decrease in the respective mean-squared displacement. By contrast, and in accordance with previous simulation studies, the present DDFT, which neglects hydrodynamic effects, shows no dependence on the particle density for this quantity.

Recently, the full phase behaviour of two-dimensional colloidal hard spheres was experimentally established, and found to involve a first order liquid to hexatic transition and a continuous hexatic to crystal transition [A. L. Thorneywork et al., Phys. Rev. Lett. 118, 158001 (2017)]. Here, we expand upon this work by considering the behaviour of the bond-orientational correlation time and Frank’s constant in the region of these phase transitions. We also consider the excess entropy, as calculated from the radial distribution functions, for a wide range of area fractions covering the liquid, hexatic and crystal phases. In all cases, the behaviour of these quantities further corroborates the previously reported melting scenario of two-dimensional colloidal hard spheres.

Alignment of anisometric particles into liquid crystals (LCs) often results from an entropic competition between their rotational and translational degrees of freedom at dense packings. Here we show that by selectively functionalizing the heads of colloidal rods with magnetic nanoparticles this tendency can be broken to direct the particles into novel, low-density LC phases. Under an external magnetic field, the magnetic heads line up in columns whereas the nonmagnetic tails point out randomly in a plane perpendicular to the columns, forming bottle-brush-like objects; laterally, the bottle brushes are entropically stabilized against coalescence. Experiments and simulations show that upon increasing the particle density the system goes from a dilute gas to a dense two-dimensional liquid of bottle brushes with a density well below the zero-field nematic phase. Our findings offer a strategy for self-assembly into three-dimensional open phases that may find applications in switchable photonics, filtration, and light-weight materials.

Understanding grain growth is key for controlling the microstructure and the mechanical properties of most polycrystalline materials, including metals, alloys, and ceramics. However, the precise mechanisms and kinetics of grain growth remain poorly understood both at the theoretical level and experimentally as direct observation is cumbersome in atomic systems. Here, we study the grain growth process in a polycrystalline monolayer of colloidal hard spheres. We find that the bond-orientational correlation function satisfies the dynamic scaling hypothesis and has the general scaling form predicted for systems containing random domain walls. However, the associated correlation length grows slower than ∼t^{1/2}, which corresponds to normal curvature-driven grain growth. To understand the origin of this anomalous grain growth, we directly monitor the evolution of the grain boundary network by measuring the so-called grain boundary character distribution. We show that there is a strong annihilation of large-angle grain boundaries while small-angle grain boundaries become relatively more present. Using scaling arguments, we derive the time dependence of the correlation length and show its good agreement with the data. We conclude that the origin of anomalous grain growth is the curvature-driven coarsening of the large-angle grain boundaries at a rate that depends on their relative length in the total grain boundary network.

Confocal microscopy was used to directly observe the structural coarsening of the first layer of short colloidal rods sedimented onto a flat wall. Based on an image analysis algorithm we devised, quantitative information on the location, orientation and length of each particle can be extracted with high precision. At high density the system undergoes structural arrest, and becomes trapped in a disordered state of randomly arranged filaments that are composed of side-by-side aligned rods. The frustration of structural order is signalled by a new peak that emerges in the radial distribution function. Configuration analysis shows that the peak is primarily due to pairs of particles that are arranged in a “T” shape, a configuration that is compatible with neither crystallization nor filament growth. Our results point to a self-poisoning mechanism for the frustration of structural order, and highlight the importance of particle shape in controlling colloidal assembly thus materials properties.

We study the melting of quasi-two-dimensional colloidal hard spheres by considering a tilted monolayer of particles in sedimentation-diffusion equilibrium. In particular, we measure the hard-disk equation of state from the density profiles and use time-dependent and height-resolved correlation functions to identify the liquid, hexatic and crystal phases. We find that the liquid-hexatic transition is first order and that the hexatic-crystal transition is continuous. Furthermore, we directly measure the width of the liquid-hexatic coexistence gap from the uctuations of the corresponding interface, and thereby experimentally establish the full phase behaviour of hard disks.

We study the freezing of a dispersion of colloidal silica particles in water, focusing on the formation of segregated ice in the form of ice lenses. Local temperature measurements in combination with video microscopy give insight into the rich variety of factors that control ice lens formation. We observe the initiation of the lenses, their growth morphology and their final thickness and spacing, over a range of conditions, in particular the effect of the particle packing and the cooling rate. We find that increasing the particle density drastically reduces the thickness of lenses, but has little effect on the lens spacing. Therefore, the fraction of segregated ice formed reduces. The effect of the cooling rate, which is the product of the temperature gradient and the pulling speed across the temperature gradient, depends on which parameter is varied. A larger temperature gradient causes ice lenses to be initiated more frequently, while a lower pulling speed allows for more time for ice lenses to grow: both increase the fraction of segregated ice. Surprisingly, we find that the growth rate of a lens does not depend on its undercooling. Finally, we have indications of pore ice in front of the warmest ice lens, which has important consequences for the interpretation of the measured trends. Our findings have important consequences for ice segregation occurring in a wide range of situations, ranging from model lab experiments and theories, to geological and industrial processes, like frost heave and frozen food production.

We investigate the role of a colloidal model system in the crystallization and network formation of lipids. This system consists of fractal fumed silica aggregates. We look at the influence of different solid fat concentrations and fumed silica concentrations on the resulting gel network. Oscillatory rheology shows that the addition of silica to fat-in-oil gels does not significantly affect the magnitude of the storage modulus within the linear viscoelastic region. Interestingly, the range of this region is increased. Differential scanning calorimetry shows that the presence of silica leads to slightly earlier crystallization, though no significant effect on the melting profile of the formed network is found. Based on these observations, we propose that composite gel network structures have been formed. These results show that we have created reduced solid fat alternatives with similar rheological behaviour and thermal properties as the full-fat systems through the addition of colloidal silica.

A binary mixture of superparamagnetic colloidal particles is confined between glass plates such that the large particles become fixed and provide a two-dimensional disordered matrix for the still mobile small particles, which form a fluid. By varying fluid and matrix area fractions and tuning the interactions between the superparamagnetic particles via an external magnetic field, different regions of the state diagram are explored. The mobile particles exhibit delocalized dynamics at small matrix area fractions and localized motion at high matrix area fractions, and the localization transition is rounded by the soft interactions [T. O. E. Skinner et al., Phys. Rev. Lett. 111, 128301 (2013)PRLTAO0031-900710.1103/PhysRevLett.111.128301]. Expanding on previous work, we find the dynamics of the tracers to be strongly heterogeneous and show that molecular dynamics simulations of an ideal gas confined in a fixed matrix exhibit similar behavior. The simulations show how these soft interactions make the dynamics more heterogeneous compared to the disordered Lorentz gas and lead to strong non-Gaussian fluctuations.

We report on the confinement of colloidal liquid crystals in three dimensional chambers with a square footprint. To this end we use colloidal silica rods and exploit their relatively large density difference with respect to the dispersing solvent to study isotropic, nematic and smectic phases confined into a single chamber. Combining laser scanning confocal microscopy and soft-lithography techniques enables us to characterize the configurations down to the single particle level. We will focus on the smectic phase and compare to recent theories and simulations.

Recent progress in synthetic nanotechnology and the ancient use of metals in food preservation and the antibacterial treatment of wounds have prompted the development of nanometallic materials for antimicrobial applications1–4. However, the materials designed so far do not simultaneously display antimicrobial activity and the capability of binding and capturing bacteria and spores. Here, we develop a one-step pyrolysis procedure to synthesize monodisperse superparamagnetic nickel colloidal nanocrystal clusters (SNCNCs), which show both antibacterial activity and the ability to bind Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as bacterial spores. The SNCNCs are formed from a rapid burst of nickel nanoparticles, which self-assemble slowly into clusters. The clusters can magnetically extract 99.99% of bacteria and spores and provide a promising approach for the removal of microbes, including hard-to-treat microorganisms. We believe that our work illustrates the exciting opportunities that nanotechnology offers for alternative antimicrobial strategies and other applications in microbiology. Monodispersed superparamagnetic nickel colloidal nanocrystal clusters synthesized by pyrolysis can capture bacteria and bacterial spores and simultaneously exert antimicrobial activity.

We investigate the segregation of impurities to grain boundaries in colloidal polycrystalline monolayers using video-microscopy. A model colloidal alloy is prepared by embedding large spherical impurities in a polycrystalline monolayer of small host colloidal hard spheres, which stops grain growth at a finite grain size. The size ratio between the impurities and the host particles determines whether they behave as interstitial or substitutional impurities in the bulk crystal, akin to those in real alloys. We find that the partitioning of impurities between the grains and the grain boundaries is in very good agreement with the Langmuir-McLean adsorption model for equilibrium grain boundary segregation. This enables the direct measurement of the free energy of adsorption for the two types of impurities. Near saturation, we characterise the spatial distribution of the adsorbed impurities and find that it strongly depends on their interstitial or substitutional nature. This is because the relative importance of clustering and mixing due to non-additivity is determined by geometrical constraints imposed by the crystalline host lattice.

We present a systematic experimental study of the dynamic behaviour of monodisperse and bidisperse two-dimensional colloidal hard sphere fluids. We consider the diffusive behaviour of the two types of particles for systems with a variety of compositions and total area fractions. In particular, we measure the short- and long-time diffusion coefficients for both species independently. We find that the short-time self-diffusion coefficients show an approximately linear dependence on the area fraction and that the long-time self-diffusion coefficients are well described by an expression dependent upon only the area fraction and contact value of the radial distribution function. Finally, we consider the effect of composition change and find some variation in the long-time self-diffusion coefficients, which we ascribe to the complex packing effects exhibited by binary systems.

We achieve active control of interfacial phenomena by optically trapping the interface using the gradient forces of a strongly focussed laser beam parallel to the interface. We illustrate our technique in a phase separated colloid-polymer mixture by distorting the interface in a very controlled way. The static structure of the manipulated interface as well as its dynamic relaxation behaviour are analysed. Both the statics and dynamics can be related to the capillary wave height-height correlation functions using the fluctuation dissipation theorem up to surprisingly large deformations of the interface. To underline the novelty and potential of our approach we also show multiple interface distortions and the controlled snap-off of liquid droplets.

Impurities affect the nucleation, growth, and structure of crystals. Here we report the effect of large, spherical, polymethylmethacrylate impurities on the crystal growth of monodisperse, hard, polymethylmethacrylate colloids in a density- and optically matching apolar solvent mixture. Crystal growth, initiated at the bottom of the sample, was studied by imaging sequences of two-dimensional xy slices in the plane of the impurity's center with a laser scanning confocal microscope. Impurities form the center of grain boundaries, and a single fluid particle layer around the impurity persists in all cases. The growth rate sensitively depends on the impurity's size. Crystal growth is inhibited to a greater extent near smaller impurities, pointing to local crystal frustration induced by the curvature of the impurity.

The crystallisation and melting behaviour of superparamagnetic colloidal particles confined within a two-dimensional pentagonal environment is studied by systematically varying either the external magnetic field or the number of particles. A system containing 16 confined particles melts monotonically from a commensurate crystalline configuration to a confined liquid-like state as the magnetic field is reduced. When the magnetic field is kept constant and the number of confined particles is increased from 11 to 21, highly non-monotonic behaviour is observed involving re-entrant structural ordering and dynamically frustrated states.

Grain boundaries are solid–solid interfaces whose dynamics is driven by their local curvature. As they are fluctuating interfaces and have a width comparable to the lattice spacing of the surrounding grains, the determination of their local geometrical characteristics is difficult. Here we present a method to determine the local normal direction, tangent plane and curvature of grain boundaries from microscopy images using point sampled surface analysis techniques. We apply our algorithm to study the boundary of a shrinking grain in a two-dimensional colloidal polycrystalline material. Our method is easily generalized to three dimensions, which makes it applicable to the wide range of interfaces encountered in soft matter.

The effect of a nonspherical particle shape and shape polydispersity on the structure of densely packed hard colloidal particles was studied in real space by confocal microscopy. We show that the first layer at the wall of concentrated size-monodisperse but shape-polydisperse polyhedral colloids exhibits significant deviations from a hexagonal lattice. These deviations are identified as bond-orientational fluctuations which lead to percolating "mismatch lines." While the shape-induced geometrical frustration of the hexagonal symmetry suppresses translational order, bond-orientational order is clearly retained, indicating a hexaticlike structure of the polyhedral colloids.

We study a small system of spherically confined hard spheres using the Widom particle insertion method as an indicator for the ordering transition. By Monte Carlo simulations we determine the insertion probability as a function of the number of particles and the box size. We find an increase of the insertion probability upon increasing density, which becomes more pronounced as the box size decreases. The increase of the insertion probability corresponds to an increase of the order, which is confirmed by a local bond-order analysis and the simulation snapshots. The ordered structures can be described as defective solids.

Direct visual observations on how grain boundaries are pinned between multiple large spherical impurities during colloidal hard sphere crystallisation are presented. The fluid is stabilized between impurities and acts as a precursor for grain boundary formation. The range of fluid stabilisation by a single impurity is characterized by the frustration length, which goes through a maximum as a function of the impurity-to-particle size ratio. Grain boundaries are more strongly confined to the area between two impurities as the ratio between the impurity-to-impurity spacing and the combined frustration lengths decreases. Our results identify the key parameters in grain boundary formation in doped systems, which may lead to a better control of the grain boundary density in materials. © The Royal Society of Chemistry 2009.

We report the observation of a new type of columnar liquid crystal phase, which is formed by thin hard colloidal disks in a dense suspension. High-resolution small-angle x-ray diffraction reveals a combination of long-range bond-orientational order and short-range translational order between the columns, the hallmark of the hexatic phase. Our results imply that geometric frustration related to the size polydispersity of the particles destroys long-range translational order and therefore promotes the formation of this novel phase.

We studied the effect of a solid surface on the fluid-fluid phase separation of a colloid-polymer mixture in real space, exploring demixing from both the unstable and metastable regions of the phase diagram. The presence of a wall breaks the symmetry of the phase separation morphology in the direction perpendicular to the surface, influencing the coarsening behavior of domains. We analyzed the thickening of the wetting layers and found that hydrodynamic transport processes can significantly increase the rate of wetting-layer growth. Depending on the volume ratio between the two phases, a new regime was observed in which the demixing structure disconnected from the wall, but remained bicontinuous in the bulk. We also discuss the effect of a crossover in the demixing regime of bulk domains on the growth of this layer.

We calculate the interfacial tension and the wetting behavior in phase separated colloid–polymer mixtures both for ideal and excluded volume interacting polymers. Within the recently developed extension of the free volume theory to include polymer interactions [Aarts, Tuinier, and Lekkerkerker, J. Phys.: Condens. Matter 14, 7551 (2002)] the interfacial tension of the free interface is calculated by adding a van der Waals squared gradient term. The wetting behavior at a hard wall is calculated following a Cahn–Fisher–Nakanishi approach taking the one- and two-body colloid-wall interactions into account. Comparing results for interacting polymers with those for ideal polymers we find that for interacting polymers the interfacial tension does not increase as steeply as a function of the gas–liquid colloid density difference. Furthermore, the wetting transition shifts to higher polymer concentrations, even to above the triple line. The predictions for both the interfacial tension and the wetting are compared to recent experiments.

© 2015 American Physical Society. We compare experimental results from a quasi-two-dimensional colloidal hard sphere fluid to a Monte Carlo simulation of hard disks with small particle displacements. The experimental short-time self-diffusion coefficient DS scaled by the diffusion coefficient at infinite dilution, D0, strongly depends on the area fraction, pointing to significant hydrodynamic interactions at short times in the experiment, which are absent in the simulation. In contrast, the area fraction dependence of the experimental long-time self-diffusion coefficient DL/D0 is in quantitative agreement with DL/D0 obtained from the simulation. This indicates that the reduction in the particle mobility at short times due to hydrodynamic interactions does not lead to a proportional reduction in the long-time self-diffusion coefficient. Furthermore, the quantitative agreement between experiment and simulation at long times indicates that hydrodynamic interactions effectively do not affect the dependence of DL/D0 on the area fraction. In light of this, we discuss the link between structure and long-time self-diffusion in terms of a configurational excess entropy and do not find a simple exponential relation between these quantities for all fluid area fractions.

The non-Newtonian properties of blood are of great importance since they are closely related with incident cardiovascular diseases. A good understanding of the hemodynamics through the main vessels of the human circulatory system is thus fundamental in the detection and especially in the treatment of these diseases. Very often such studies take place in vitro for convenience and better flow control and these generally require blood analogue solutions that not only adequately mimic the viscoelastic properties of blood but also minimize undesirable optical distortions arising from vessel curvature that could interfere in flow visualizations or particle image velocimetry measurements. In this work, we present the viscoelastic moduli of whole human blood obtained by means of passive microrheology experiments. These results and existing shear and extensional rheological data for whole human blood in the literature enabled us to develop solutions with rheological behavior analogous to real whole blood and with a refractive index suited for PDMS (polydymethylsiloxane) micro-and milli-channels. In addition, these blood analogues can be modified in order to obtain a larger range of refractive indices from 1.38 to 1.43 to match the refractive index of several materials other than PDMS. (C) 2013 AIP Publishing LLC.

Paramagnetic colloidal particles that are optically trapped in a linear array can form a zigzag pattern when an external magnetic field induces repulsive interparticle interactions. When the traps are abruptly turned off, the particles form a nonequilibrium expanding pattern with a zigzag symmetry, even when the strength of the magnetic interaction is weaker than that required to break the linear symmetry of the equilibrium state. We show that the transition to the equilibrium zigzag state is always potentially possible for purely harmonic traps. For anharmonic traps that have a finite height, the equilibrium zigzag state becomes unstable above a critical anharmonicity. A normal mode analysis of the equilibrium line configuration demonstrates that increasing the magnetic field leads to a hardening and softening of the spring constants in the longitudinal and transverse directions, respectively. The mode that first becomes unstable is the mode with the zigzag symmetry, which explains the symmetry of nonequilibrium patterns. Our analytically tractable models help to give further insight into the way that the interplay of such factors as the length of the chain, hydrodynamic interactions, thermal fluctuations affect the formation and evolution of the experimentally observed nonequilibrium patterns., Comment: 16 pages, 8 figures; to appear in the Journal of Chemical Physics