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We used mixture design to predict rheological parameters, namely the storage and loss modulus $$G'$$ G ′ and $$G''$$ G ′ ′ and the critical stress $$\sigma _{c}$$ σ c , of mixtures of Laponite EP and bentonite clay. Laponite EP is an organically coated laponite displaying unusual rheological behaviour compared to its unmodified form. We examined the effect of salt (magnesium chloride) and of surfactant (Tween 20) varying the pH between 4 and 9. We found reliable complex models with significant higher order terms showing that the rheological behaviour of the gels was not a function of each single compound, but instead the result of multiple interactions. Such interactions had an antagonistic effect on $$G'$$ G ′ and $$G''$$ G ′ ′ . Stronger gels were found at low concentrations of magnesium chloride and Tween 20. The gel stability in response to stress increased with the amount of Tween 20, but decreased with magnesium chloride. Such distinct behaviour may be the result of interactions between the platelet charges and the different components, as well as salting in versus salting out effects. We identified the conditions for which the values of $$G'$$ G ′ were suitable for agrochemical products. The method presented here is a quick and reliable approach to formulate products with targeted rheological properties.

The two-dimensional Active Brownian Particles system is meant to be composed of hard disks, that show excluded volume interactions, usually simulated via molecular dynamics using pure repulsive potentials. We show that the softness of the chosen potential plays a role in the result of the simulation, focusing on the case of the emergence of Motility Induced Phase Separation. In a pure hard-sphere system with no traslational diffusion,the phase diagram should be completely determined by their density and P\'eclet number. However, we have found two additional effects that affect the phase diagram in the ABP model we simulate: the relative strength of the traslational diffusion compared to the propulsion term and the overlapping of the particles. As we show, the second effect can be strongly mitigated if we use, instead of the standard Weeks-Chandler- Andersen potential, a harder one, the pseudo-hard spheres potential. Moreover, in determining the boundary of our phase space, we have tried different approaches to detect MIPS and concluded that observing dynamical features, via the non-Gaussian parameter, is more efficient than observing structural ones, via the local density distribution function. We also demonstrate that the Vogel-Fulcher equation successfully reproduces the decay of the diffusion as a function of density, except for very high density cases. Thus, the ABP system behaves similarly to a fragile glass in this regard.

We determined the phase boundaries of aqueous mixtures containing colloidal rod-like \textit{fd}-viruses and polystyrene spheres using diffusing-wave spectroscopy and compared the results with free volume theory predictions. Excluded volume interactions in mixtures of colloidal rods and spheres lead to mediated depletion interactions. The strength and range of this attractive interaction depend on the concentrations of the particles, the length $L$ and diameter $D$ of the rods and the radius $R$ of the spheres. At strong enough attraction, this depletion interaction leads to phase separation. We experimentally determined the rod and sphere concentrations where these phase transitions occur by systematically varying the size ratios $L/R$ and $D/R$ and the aspect ratio $L/D$. This was done by using spheres with different radii and modifying the effective diameter of the rods through either the ionic strength of the buffer or anchoring a polymeric brush to the surface of the rods. The observed phase transitions were from a binary fluid to a colloidal gas/liquid phase coexistence which occurred already at very low concentrations due to the depletion efficiency of highly anisotropic rods. The experimentally measured phase transitions were compared to phase boundaries obtained using free volume theory (FVT), a well established theory for calculating the phase behaviour of colloidal particles mixed with depletants. We find good correspondence between the experimental phase transitions and the theoretical FVT model where the excluded volume of the rod-like depletants was explicitly accounted for in both the reservoir and the system.

We propose a general formalism to characterize orientational frustration of smectic liquid crystals in confinement by interpreting the emerging networks of grain boundaries as objects with a topological charge. In a formal idealization, this charge is distributed in point-like units of quarter-integer magnitude, which we identify with tetratic disclinations located at the end points and nodes. This coexisting nematic and tetratic order is analyzed with the help of extensive Monte Carlo simulations for a broad range of two-dimensional confining geometries as well as colloidal experiments, showing how the observed defect networks can be universally reconstructed from simple building blocks. We further find that the curvature of the confining wall determines the anchoring behavior of grain boundaries, such that the number of nodes in the emerging networks and the location of their end points can be tuned by changing the number and smoothness of corners, respectively., To appear in Physical Review Letters

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.

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.

Certain pairs of paramagnetic species generated under conservation of total spin angular momentum are known to undergo magnetosensitive processes. Two prominent examples of systems exhibiting these so-called magnetic field effects (MFEs) are photogenerated radical pairs created from either singlet or triplet molecular precursors, and pairs of triplet states generated by singlet fission. Here, we showcase confocal microscopy as a powerful technique for the investigation of such phenomena. We first characterise the instrument by studying the field-sensitive chemistry of two systems in solution: radical pairs formed in a cryptochrome protein and the flavin mononucleotide/hen egg-white lysozyme model system. We then extend these studies to single crystals. Firstly, we report temporally and spatially resolved MFEs in flavin-doped lysozyme single crystals. Anisotropic magnetic field effects are then reported in tetracene single crystals. Finally, we discuss the future applications of confocal microscopy for the study of magnetosensitive processes with a particular focus on the cryptochrome-based chemical compass believed to lie at the heart of animal magnetoreception., Confocal microscopy is showcased as a powerful technique for the measurement of spatiotemporally-resolved magnetic field effects in both solutions and single crystals.

The opportunistic pathogen Pseudomonas aeruginosa is a major cause of antibiotic-tolerant infections in humans. P. aeruginosa evades antibiotics in bacterial biofilms by up-regulating expression of a symbiotic filamentous inoviral prophage, Pf4. We investigated the mechanism of phage-mediated antibiotic tolerance using biochemical reconstitution combined with structural biology and high-resolution cellular imaging. We resolved electron cryomicroscopy atomic structures of Pf4 with and without its linear single-stranded DNA genome, and studied Pf4 assembly into liquid crystalline droplets using optical microscopy and electron cryotomography. By biochemically replicating conditions necessary for antibiotic protection, we found that phage liquid crystalline droplets form phase-separated occlusive compartments around rod-shaped bacteria leading to increased bacterial survival. Encapsulation by these compartments was observed even when inanimate colloidal rods were used to mimic rod-shaped bacteria, suggesting that shape and size complementarity profoundly influences the process. Filamentous inoviruses are pervasive across prokaryotes, and in particular, several Gram-negative bacterial pathogens including Neisseria meningitidis , Vibrio cholerae, and Salmonella enterica harbor these prophages. We propose that biophysical occlusion mediated by secreted filamentous molecules such as Pf4 may be a general strategy of bacterial survival in harsh environments.

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 planar nematic equilibria on a two-dimensional annulus with strong and weak tangent anchoring, in the Oseen–Frank theoretical framework. We analyze a radially invariant defect-free state and compute analytic stability criteria for this state in terms of the elastic anisotropy, annular aspect ratio, and anchoring strength. In the strong anchoring case, we define and characterize a new spiral-like equilibrium which emerges as the defect-free state loses stability. In the weak anchoring case, we compute stability diagrams that quantify the response of the defect-free state to radial and azimuthal perturbations. We study sector equilibria on sectors of an annulus, including the effects of weak anchoring and elastic anisotropy, giving novel insights into the correlation between preferred numbers of boundary defects and the geometry. We numerically demonstrate that these sector configurations can approximate experimentally observed equilibria with boundary defects.

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 study the orientational dynamics of heavy silica microrods flowing through a microfluidic channel. Comparing experiments and Brownian dynamics simulations we identify different particle orbits, in particular in-plane tumbling behavior, which cannot be explained by classical Jeffery theory, and we relate this behavior to the rotational diffusion of the rods. By constructing the full, three-dimensional, orientation distribution, we describe the rod trajectories and quantify the persistence of Jeffery orbits using temporal correlation functions of the Jeffery constant. We find that our colloidal rods lose memory of their initial configuration in about a second, corresponding to half a Jeffery period.

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.

Gelation processes grant access to a wealth of soft materials with tailorable properties, in applications as diverse as environmental remediation, biomedicene and electronics. Several classes of self-assembling gelators have been studied and employ non-covalent bonds to direct assembly, but recently attention has come to focus on how the overall shape of the gelator molecule impacts its gelation. Here we study a new sub-family of low molecular weight organogelators and explore how steric rearrangement influences their gelation. The gels produced are characterised with X-ray diffraction and Small- Angle neutron scattering (SANS) to probe their ex-situ and in-situ gelation mechanisms. The best examples were then tested for environmental remediation applications, gelling petrol and oils in the presence of water and salts.

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.

When a liquid crystal forming particles are confined to a spatial volume with dimensions comparable to that of their own size, they face a complex trade-off between their global tendency to align and the local constraints imposed by the boundary conditions. This interplay may lead to a non-trivial orientational patterns that strongly depend on the geometry of the confining volume. This novel regime of liquid crystalline behavior can be probed with colloidal particles that are macro-aggregates of biomolecules. Here we study director fields of filamentous fd-viruses in quasi-2D lens-shaped chambers that mimic the shape of tactoids, the nematic droplets that form during isotropic-nematic phase separation. By varying the size and aspect ratio of the chambers we force these particles into confinements that vary from circular to extremely spindle-like shapes and observe the director field using fluorescence microscopy. In the resulting phase diagram, next to configurations predicted earlier for 3D tactoids, we find a number of novel configurations. Using Monte Carlo Simulations, we show that these novel states are metastable, yet long-lived. Their multiplicity can be explained by the co-existence of multiple dynamic relaxation pathways leading to the final stable states.

When a capillary is half-filled with liquid and turned to the horizontal, the liquid may flow out of the capillary or remain in it. For lack of a better criterion, the standard assumption is that the liquid will remain in a capillary of narrow cross-section, and will flow out otherwise. Here, we present a precise mathematical criterion that determines which of the two outcomes occurs for capillaries of arbitrary cross-sectional shape, and show that the standard assumption fails for certain simple geometries, leading to very rich and counterintuitive behavior. This opens the possibility of creating very sensitive microfluidic devices that respond readily to small physical changes, for instance, by triggering the sudden displacement of fluid along a capillary without the need of any external pumping. We thank Eduardo Colorado for insightful comments. C.R. acknowledges the support of the Spanish Ministerio de Economía y Competitividad under Grant FIS2015 66523 P.

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

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.

We study the azimuthal defect-free nematic state on a two-dimensional annulus within a simplified and reduced two-dimensional Landau--de Gennes model for nematic liquid crystals. We perform a detailed asymptotic analysis of the instabilities of the defect-free state in terms of a dimensionless material and temperature-dependent variable and the annular aspect ratio. The asymptotic analysis is accompanied by a rigorous local stability result, again in terms of a dimensionless material and temperature-dependent parameter and annular aspect ratio. In contrast to Oseen--Frank predictions, the defect-free state can be unstable in this model, with elastic isotropy and strong anchoring, for a range of macroscopically relevant annular aspect ratios.

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 theoretically and experimentally study nematic liquid crystal equilibria within shallow rectangular wells. We model the wells within a two-dimensional Oseen-Frank framework, with strong tangent anchoring, and obtain explicit analytical expressions for the director fields and energies of the 'diagonal' and 'rotated' solutions reported in the literature. These expressions separate the leading-order defect energies from the bulk distortion energy for both families of solutions. The continuum Oseen-Frank study is complemented by a microscopic mean-field approach. We numerically minimize the mean-field functional, including the effects of weak anchoring, variable order and random initial conditions. In particular, these simulations suggest the existence of higher-energy metastable states with internal defects. We compare our theoretical results to experimental director profiles, obtained using two types of filamentous virus particles, wild-type fd-virus and a modified stiffer variant (Y21M), which display nematic ordering in rectangular chambers, as found by confocal scanning laser microscopy. We combine our analytical energy expressions with experimentally recorded frequencies of the different equilibrium states to obtain explicit estimates for the extrapolation length, defined to be the ratio of the nematic elastic constant to the anchoring coefficient, of the fd-virus. crosscheck: This document is CrossCheck deposited copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal copyright_licence: The accepted version of this article will be made freely available after a 12 month embargo period history: Received 23 May 2014; Accepted 23 July 2014; Accepted Manuscript published 23 July 2014; Advance Article published 26 August 2014; Version of Record published 17 September 2014 ispartof: Soft Matter vol:10 issue:39 pages:7865-7873 ispartof: location:England status: published

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 investigate the off-critical demixing of colloid-polymer systems confined between two parallel plates, where the surface potential is short ranged. We study the case where the minority phase completely wets the surfaces. We find that initially the sample separates as in bulk, until the size of the domains becomes sufficiently large such that further growth is restricted by the plate spacing. The behaviour of the droplets is then determined by the wettability of the walls. We furthermore explore a sample where the loss of wetting phase material to the surfaces causes a shift from a morphology associated with an unstable sample, showing spinodal decomposition, to that associated with a metastable sample. This underlines the importance of the rich interplay between the viscosity contrast and the local volume fraction on the observed morphologies.

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.

We study the demixing via spinodal decomposition of a fluid-fluid phase separating colloid-polymer mixture confined between parallel plates, where one of the phases completely wets both walls. Using confocal scanning laser microscopy, we are able to obtain real space images, both parallel and perpendicular to the cell walls. We observe three distinct morphologies: the formation of a bicontinuous network, which coarsens into cylindrical tubes bridging the plates, and finally develops into a network structure in two dimensions. Through image analysis of the system as a whole, and the tracking of individual domains, we are able to perform a detailed study of the mechanisms of phase coarsening at each stage. We are able to directly test the condition for which bridges connecting both confining walls do not sever. Finally, we consider the role of hydrodynamics and of thermal interface fluctuations in our system.

When liquid crystals are confined to finite volumes, the competition between the surface anchoring imposed by the boundaries and the intrinsic orientational symmetry-breaking of these materials gives rise to a host of intriguing phenomena involving topological defect structures. For synthetic molecular mesogens, like the ones used in liquid-crystal displays, these defect structures are independent of the size of the molecules and well described by continuum theories. In contrast, colloidal systems such as carbon nanotubes and biopolymers have micron-sized lengths, so continuum descriptions are expected to break down under strong confinement conditions. Here, we show, by a combination of computer simulations and experiments with virus particles in tailor-made disk- and annulus-shaped microchambers, that strong confinement of colloidal liquid crystals leads to novel defect-stabilized symmetrical domain structures. These finite-size effects point to a potential for designing optically active microstructures, exploiting the as yet unexplored regime of highly confined liquid crystals., Liquid crystals confined to micrometre-sized geometries can be well described by a continuum theory, where the size effect of constituent mesogens is negligible. Here, the authors show how the continuum theory breaks down in colloidal liquid crystal, leading to the formation of defect-mediated domains.

We studied the structure of a colloid-polymer mixture, in the one-phase region, as a function of polymer concentration. Using confocal microscopy, and Fourier transformation of the image data, we accessed the system in real and reciprocal space simultaneously, at the single particle level. We found no change in the colloidal fluid structure as a function of polymer concentration. The fluid phase persisted to higher concentrations of polymer than expected, before an abrupt gelation transition. Furthermore, we found a dramatic change in the local structure around each particle at the onset of gelation. We attribute these phenomena to a screened electrostatic repulsion between the colloids, which, although weak, suppressed the depletion attraction due to the polymer. The repulsive and attractive interactions have a similar range, which results in behaviour distinct both from pure depletion and the recently observed cluster phase formed in the presence of long-ranged electrostatic repulsions. Instead, these results are qualitatively similar to the competition between van der Waals and electrostatic interactions in the Derjaguin-Landau-Verwey-Overbeek theory. We compare our experiments with Monte Carlo simulation and find agreement with a combination of the Asakura-Oosawa-Vrij and Yukawa potentials. © 2005 IOP Publishing Ltd.