The design of complex materials and the formation of specific patterns often arise from the properties of the individual building blocks. In this respect, colloidal systems offer a unique opportunity because nowadays they can be synthesized in the laboratory with many different shapes and features. Hence, an appropriate choice of the particle characteristics makes it possible to generate macroscopic structures with desired properties. The versatility of colloids can also be explored in two dimensions, using liquid-liquid or air-liquid interfaces as privileged substrates where they can adsorb and self-assemble. Besides being innovative model systems for fundamental studies, the great interest of the scientific community is also technological and applicative, since colloidal-scale surface patterns are very promising for example in photonics or biosensing. In a recent study published in PNAS, Menath and coworkers combine these elements and exploit core-shell colloids, consisting of a silica core and a soft, non-crosslinked polymer shell, to make an important step forward in controlling the assembly of complex structures at an interface.
We combine experiments, theory, and simulations to investigate the coexistence of nonequilibrium phases emerging from interacting colloidal particles that are electrokinetically propelled in a nematic liquid crystal solvent. We directly determine the mechanical pressure within the radial assemblies and measure a non-equilibrium equation of state for this athermal driven system. A generic model combines phoretic propulsion with the interplay between electrostatic effects and liquid-crystal-mediated hydrodynamics, which are effectively cast into a long-range interparticle repulsion, while elasti…
Depletion interactions arise from entropic forces, and their ability to induce aggregation and even ordering of colloidal particles through self-assembly is well established, especially for spherical colloids. We vary the size and concentration of penetrable hard sphere depletants in a system of cuboctahedra, and we show how depletion changes the preferential facet alignment of the colloids and thereby selects different crystal structures. Moreover, we explain the cuboctahedra phase behavior using perturbative free energy calculations. We find that cuboctahedra can form a stable simple cubic p…
Patchy colloidal platelets with convex, non-spherical shapes have been realized with different materials at length scales ranging from nanometers to microns. While the assembly of these hard shapes tends to maximize edge-to-edge contacts, as soon as a directional attraction is added -- by means of, e.g., specific ligands along the particle edges -- a competition between shape and bonding anisotropy sets in, giving rise to a complex assembly scenario. We focus here on a two-dimensional system of patchy rhombi, i.e., colloidal platelets with a regular rhombic shape decorated with bonding sites a…
Silica nanoparticles trapped at air-water interface form a 2D solid state with amorphous order. We propose a theoretical model to describe how this solid-like state deforms under a shear strain ramp up to and beyond a yielding point which leads to plastic flow. The model accounts for all the particle-level and many-body physics of the system: nonaffine displacements, local connectivity and its evolution in terms of cage-breaking, and interparticle interactions mediated by the particle chemistry and colloidal forces. The model is able to reproduce experimental data with only two non-trivial fit…
Disordered dielectrics with structural correlations on length scales comparable to visible light wavelengths exhibit complex optical properties. Such materials exist in nature, leading to beautiful structural non-iridescent color, and they are also increasingly used as building blocks for optical materials and coatings. In this article, we study the single-scattering properties of micron-sized, disordered colloidal assemblies. The aggregates act as structurally colored supraparticles or as building blocks for macroscopic photonic glasses. We present experimental data for the differential scatt…
The propagation of chirality across scales is a common but poorly understood phenomenon in soft matter. In this work, we use computer simulations to study chiral monolayer assemblies formed by hard rod-like colloidal particles in the presence of non-adsorbing polymer and characterize the thermodynamic driving forces responsible for the twisting. Simulations show that straight (achiral) rods assemble into monolayers with a spontaneous twist that is either left- or right-handed, while helical (chiral) rods lead to assemblies with preferential chiral features that depend on their handedness and c…
The postulate of the existence of a jamming phase diagram (Liu and Nagel, Nature 396, 21 EP (1998aa)) provides a theoretical basis for the classification of a wide range of amorphous solids (colloidal, molecular and emulsion glasses, colloidal and polymer gels, foams and granular matter) on the basis of whether these materials are in the jammed or unjammed state. Whilst such simple classification is appealing, it fails to capture that the criterion of rigidity of such amorphous solids may be defined with respect to a particular deformation orientation or mode (i.e. shear, extrusion, consolidat…
Application of Machine Learning for the Identification of 2D Colloidal Assemblies: A Case Study on Particles of Distinct Shapes
Astrakhan Tatishchev State University（阿斯特拉罕塔季谢夫国立大学）；Caspian Institute of Maritime and River Transport named after Admiral General F.M. Apraksin – the affiliation of “Volga State University of Water Transport”（以海军上将F.M.阿普拉克辛命名的里海海事和河运学院——伏尔加水运大学下属机构）
Insight in the structure of nanoparticle assemblies up to a single particle level is key to understand the collective properties of these assemblies, which critically depend on the individual particle positions and orientations. However, the characterization of large, micron sized assemblies containing small, 10-500 nanometer, sized colloids is highly challenging and cannot easily be done with the conventional light, electron or X-ray microscopy techniques. Here, we demonstrate that focused ion beam-scanning electron microscopy (FIB-SEM) tomography in combination with image processing enables …
Spontaneous emulsification, resulting from the assembly and accumulation of surfactants at liquid-liquid interfaces, is an interfacial instability where microdroplets are generated and diffusively spread from the interface until complete emulsification. Here, we show that an external magnetic field can modulate the assembly of paramagnetic nanoparticle surfactants (NPSs) at liquid-liquid interfaces and trigger an oversaturation in the areal density of the NPSs at the interface, as evidenced by a marked reduction in the interfacial tension, γ, and corroborated with a magnetostatic continuum the…
We study experimentally a sediment of self-propelled Brownian particles with densities ranging from dilute to ergodic supercooled, to nonergodic glass, to nonergodic polycrystal. In a compagnon letter, we observe a nonmonotonic response to activity of relaxation of the nonergodic glass state: a dramatic slowdown when particles become weakly self-propelled, followed by a speedup at higher activities. Here we map ergodic supercooled states to standard passive glassy physics, provided a monotonic shift of the glass packing fraction and the replacement of the ambient temperature by the effective t…
Biological cells self-organize into living materials that uniquely blend structure with functionality and responsiveness to the environment. The integration of similar life-like features in man-made materials remains challenging, yet desirable to manufacture active, adaptive and autonomous systems. Here we show the self-organization of programmable random lasers from the reversible out-of-equilibrium self-assembly of colloids. Random lasing originates from the optical amplification of light undergoing multiple scattering within the dissipative colloidal assemblies and therefore is crucially de…
Interfacial undercooling is of significant importance on microscopic pattern formation in the solidification of colloidal suspensions. Two kinds of interfacial undercooling are supposed to be involved in freezing colloidal suspensions, i.e. solute constitutional supercooling (SCS) caused by additives in the solvent and particulate constitutional supercooling (PCS) caused by particles. However, quantitatively identification of the interfacial undercooling of freezing colloidal suspensions is still absent and it is still unknown which undercooling is dominant. The revealing of interfacial underc…
We use the dynamic length and time scale separation in suspensions to formulate a general description of colloidal thermophoresis. Our approach allows an unambiguous definition of separate contributions to the colloidal flux and clarifies the physical mechanisms behind non-equilibrium motion of colloids. In particular, we derive an expression for the interfacial force density that drives single-particle thermophoresis in non-ideal fluids. The issuing relations for the transport coefficients explicitly show that interfacial thermophoresis has a hydrodynamic character that cannot be explained by…
Melanin is a ubiquitous natural pigment that exhibits broadband absorption and high refractive index. Despite its widespread use in structural color production, how the absorbing material, melanin, affects the generated color is unknown. Using a combined molecular dynamics and finite-difference time-domain computational approach, this paper investigates structural color generation in one-component melanin nanoparticle-based supra-assemblies (called supraballs) as well as binary mixtures of melanin and silica (non-absorbing) nanoparticle-based supraballs. Experimentally produced one-component m…
A fresh approach to the data from experiments with hard sphere colloids yields seminal insights into the glass transition. The precise determination of the fraction of particles caged by their neighbours is unprecedented and provides cornerstone of our study. We show that the so-called "dramatic slowing" that accompanies super-packing is due to correlated cage fluctuations, rather than caging per se. Their statistics establish that the amorphous assemblies of caged particles are in states of self-organised criticality. The implied connection between the onset of caging and the thermodynamic 1s…
Using fluorescence microscopy we study the adsorption of single latex microparticles at a water/water interface between demixing aqueous solutions of polymers, generally known as a water-in-water emulsion. Similar microparticles at the interface between molecular liquids have exhibited an extremely slow relaxation preventing the observation of expected equilibrium states. This phenomenon has been attributed to "long-lived" metastable states caused by significant energy barriers $Δ{\cal F}\sim γA_d\gg k_B T$ induced by high interfacial tension ($γ\sim 10^{-2}$ N/m) and nanoscale surface defects…
Stabilization and dispersion of electrical charge by colloids in non-polar media, such as nano-particles or inverse micelles, is significant for a variety of chemical and technological applications, ranging from drug delivery to e-ink. Many applications require knowledge about concentrations near the solid|liquid interface and the bulk, particularly in media where colloids exhibit spontaneous charging properties. By modification of the mean field equations to include the finite size effects that are typical in concentrated electrolytes along with disproportionation kinetics, and by considering…
Gas-liquid phase separation in oppositely charged colloids: stability and interfacial tension
采用蒙特卡罗模拟研究了直径为s的带相反电荷的硬球屏蔽库仑（Yukawa）限制原始模型（YRPM）的相行为和界面张力。通过自由能计算和巨正则蒙特卡罗模拟，我们确定了不同的反德拜屏蔽长度k的气-液和气-固相变。我们发现，当k s <= 4时，气液两相分离是稳定的，且临界温度随相互作用屏蔽的增加（减小相互作用范围）而降低.此外，我们使用巨正则蒙特卡罗模拟确定气液界面张力。界面张力随着相互作用范围的增大而减小。特别是，我们发现，简单的缩放可以用来将界面张力的YRPM的限制原始模型，其中粒子相互作用与裸库仑相互作用。
Living microorganisms in confined systems typically experience an affinity to populate boundaries. The reason for such affinity to interfaces can be a combination of their directed motion and hydrodynamic interactions at distances larger than their own size. Here we will show that self-propelled Janus particles (polystyrene particles partially coated with platinum) immersed in droplets of water and hydrogen peroxide tend to accumulate in the vicinity of the liquid/gas interface. Interestingly, the interfacial accumulation occurs despite the presence of an evaporation-driven flow caused by a so…
Bicontinuous Pickering emulsions (bijels) are a physically interesting class of soft materials with many potential applications including catalysis, microfluidics and tissue engineering. They are created by arresting the spinodal decomposition of a partially-miscible liquid with a (jammed) layer of interfacial colloids. Porosity $L$ (average interfacial separation) of the bijel is controlled by varying the radius ($r$) and volume fraction ($ϕ$) of the colloids ($L \propto r/ϕ$). However, to optimize the bijel structure with respect to other parameters, e.g. quench rate, characterizing by $L$ a…
The effects of contact-line pinning are well-known in macroscopic systems, but are only just beginning to be explored at the microscale in colloidal suspensions. We use digital holography to capture the fast three-dimensional dynamics of micrometer-sized ellipsoids breaching an oil-water interface. We find that the particle angle varies approximately linearly with the height, in contrast to results from simulations based on minimization of the interfacial energy. Using a simple model of the motion of the contact line, we show that the observed coupling between translational and rotational degr…
