We explore the microstructure and phase behavior of confined soft colloids which can actively switch their interactions at a predefined kinetic rate. For this, we employ a reaction-diffusion approach based on a reactive dynamical density-functional theory (R-DDFT) and study the effect of a binary (two-state) switching of the size of colloids interacting with a Gaussian pair potential. The rate of switching interpolates between a near-equilibrium binary Gaussian mixture at low rates and an effective monodisperse liquid for large rates, hence strongly affecting the one-body density profiles, adsorption, and pressure at confining walls. Importantly, we demonstrate that sufficiently fast switching impedes the phase separation of an (in equilibrium) unstable liquid, allowing the dynamic control of the degree of mixing/condensation and local micro-structuring in a cellular confinement by tuning the switching rate.
We theoretically investigate general properties of driven (sheared) colloidal suspensions in confinement, based on methods of classical density functional theory. In the absence of an exact closed (Smoluchowski-) equation for the one-particle density under shear, we formulate a set of general conditions for approximations, and show that a simple closure fulfills them. The exact microscopic stress tensor is identified. Exemplifying the situation near a wall (oriented parallel to the direction of shear), we note that the microscopic shear stress is not necessarily homogeneous. Formulating a seco…
Control of physical behaviors of nematic colloids and colloidal crystals has been demonstrated by tuning particle shape, topology, chirality and surface charging. However, the capability of altering physical behaviors of such soft matter systems by changing particle shape and the ensuing responses to external stimuli has remained elusive. We fabricated genus-one nematic elastomeric colloidal ring-shaped particles and various microstructures using two-photon photopolymerization. Nematic ordering within both the nano-printed particle and the surrounding medium leads to anisotropic responses and …
We study how varying the P éclet number (Pe) affects the steady state sedimentation of colloidal particles that interact through short-ranged attractions. By employing a hybrid molecular dynamics simulation method we demonstrate that the average sedimentation velocity changes from a non- monotonic dependence on packing fraction ϕ at low Pe numbers, to a monotonic decrease with ϕ at higher Pe numbers. At low Pe number the pair correlation functions are close to their equilibrium values, but as the Pe number increases, important deviations from equilibrium forms are observed. Although the attrac…
This paper describes an experimental study of filtration of a colloidal suspension using microfluidic devices. A suspension of micrometer-scale colloids flows through parallel slit-shaped pores at fixed pressure drop. Clogs and cakes are systematically observed at pore entrance, for variable applied pressure drop and ionic strength. Based on image analysis of the layer of colloids close to the device wall, global and local studies are performed to analyse in detail the near-wall layer microstructure. Whereas global porosity of this layer does not seem to be affected by ionic strength and appli…
We demonstrate that nature has produced a close-packed helical twisted filamentous material in the biomineralization of the mollusc. In liquid crystals, twist-bend nematics have been predicted and observed. We present and analyse evidence that the helical biomineral microstructure of mollusc shells may be formed from such a liquid-crystal precursor.
The ability to control the crystallization behaviour (including its absence) of particles, be they biomolecules such as globular proteins, inorganic colloids, nanoparticles, or metal atoms in an alloy, is of both fundamental and technological importance. Much can be learnt from the exquisite control that biological systems exert over the behaviour of proteins, where protein crystallization and aggregation are generally suppressed, but where in particular instances complex crystalline assemblies can be formed that have a functional purpose. We also explore the insights that can be obtained from…
Optical tweezers (OTs) can detect pico-Newton range forces operating on a colloidal particle trapped in a medium and have been successfully utilized to investigate complex systems with internal structures. Laponite clay particles in an aqueous medium self-assemble to form microscopic networks over time as electrostatic interactions between the particles gradually evolve in a physical aging process. We investigate the forced movements of an optically trapped micron-sized colloidal probe particle, suspended in an aging Laponite suspension, as the underlying Laponite microstructures gradually dev…
Using a novel bi-axial confocal rheoscope, we investigate the structure and rheology of sheared colloidal suspensions under confinement. Consistent with previous work [X. Cheng \textit{et al., Proc. Natl. Acad. Sci. U. S. A.}, 2011, 109, 63], we observe a vorticity-aligned string phase in moderate concentrated colloidal suspensions under uniaxial shear. Using bi-axial shear protocols, we directly manipulate the orientation and morphology of the string structures. Simultaneously, we measure the suspension rheology along both the flow and vorticity directions with a bi-axial force measurement de…
From suspensions to porous multilayers: microstructure formation and particle packing in drying colloidal films
Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Forschungszentrum Jülich（于利希研究中心埃尔朗根-纽伦堡亥姆霍兹可再生能源研究所（IET-2））；Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡弗里德里希·亚历山大大学）
Employing a recently developed dynamical density functional theory we study the response of a colloidal sediment above a wall to shear, demonstrating the time dependent changes of the density distribution and its center-of-mass after switching shear either on or off and under oscillatory shear. Following the onset of steady shear we identify two dynamical mechanisms, distinguished by their timescales. Shortly after the onset, a transient enhancement of the packing structure at the wall reflects the self-organization into lanes. On a much longer timescale these effects are transmitted to the bu…
Low-density "equilibrium" gels that consist of a percolated, kinetically arrested network of colloidal particles and are resilient to aging can be fabricated by restricting the number of effective bonds that form between the colloids. Valence-restricted patchy particles have long served as one archetypal example of such materials, but equilibrium gels can also be realized through a synthetically simpler and scalable strategy that introduces a secondary linker, such as a small ditopic molecule, to mediate the bonds between the colloids. Here, we consider the case where the ditopic linker molecu…
Minimal models of active Brownian colloids consisting of self-propelled spherical particles with purely repulsive interactions have recently been identified as excellent quantitative testing grounds for theories of active matter and have been the subject of extensive numerical and analytical investigation. These systems do not exhibit aligned or flocking states, but do have a rich phase diagram, forming active gases, liquids and solids with novel mechanical properties. This article reviews recent advances in the understanding of such models, including the description of the active gas and its …
Placing colloidal particles in predesigned sites represents a major challenge of the current state-of-the-art colloidal science. Nematic liquid crystals with spatially varying director patterns represent a promising approach to achieve a well-controlled placement of colloidal particles thanks to the elastic forces between the particles and the surrounding landscape of molecular orientation. Here we demonstrate how the spatially varying director field can be used to control placement of non-spherical particles of boomerang shape. The boomerang colloids create director distortions of a dipolar s…
The critical Casimir effect provides a thermodynamic analogue of the well-known quantum mechanical Casimir effect. It acts between two surfaces immersed in a critical binary liquid mixture, and results from the confinement of concentration fluctuations of the solvent. Unlike the quantum mechanical effect, the magnitude and range of this attraction can be adjusted with temperature via the solvent correlation length, thus offering new opportunities for the assembly of nano and micron-scale structures. Here, we demonstrate the active assembly control of equilibrium phases using critical Casimir f…
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…
By employing monomer-resolved computer simulations and analytical considerations based on polymer scaling theory, we analyze the conformations and interactions of multiarm star polymers strongly adsorbed on a smooth, two-dimensional plane. We find a stronger stretching of the arms as well as a stronger repulsive, effective interaction than in the three dimensional case. In particular, the star size scales with the number of arms $f$ as $\sim f^{1/4}$ and the effective interaction as $\sim f^{2}$, as opposed to $\sim f^{1/5}$ and $\sim f^{3/2}$, respectively, in three dimensions. Our results de…
We propose a new strategy to improve the self-assembly properties of DNA-functionalised colloids. The problem that we address is that DNA-functionalised colloids typically crystallize in a narrow temperature window, if at all. The underlying reason is the extreme sensitivity of DNA-mediated interactions to temperature or other physical control parameters. We propose to widen the window for colloidal crystallization by exploiting the competition between DNA linkages with different nucleotide sequences, which results in a temperature-dependent switching of the dominant bond type. Following such …
Particle-tracking microrheology of dilute active (self-propelled) colloidal suspensions is studied by considering the external force required to maintain the steady motion of an immersed constant-velocity colloidal probe. If the probe speed is zero, the suspension microstructure is isotropic but exhibits a boundary accumulation of active bath particles at contact due to their self-propulsion. As the probe moves through the suspension, the microstructure is distorted from the nonequilibrium isotropic state, which allows us to define a microviscosity for the suspension using the Stokes drag law.…
Colloidal gels formed from small attractive particles are commonly used in formulations to keep larger components in suspension. However, despite extensive work characterizing unfilled gels, little is known about how larger inclusions alter the phase behavior and microstructure of the colloidal system. Here we use numerical simulations to examine how larger `granular' particles can alter the gel transition phase boundaries. We find two distinct regimes depending on both the filler size and native gel structure: a `passive' regime where the filler fits into already-present voids, giving little …
Steering Active-Colloid Assembly by Biasing Dissipation
University of Science and Technology of China（中国科学技术大学）；Rice University（莱斯大学）；Hefei National Research Center for Physical Sciences at the Microscale（合肥微尺度物质科学国家研究中心）
Composite colloidal assembly by critical Casimir forces
University of Amsterdam（阿姆斯特丹大学）；Wageningen University and Research（瓦赫宁根大学和研究机构）；Polish Academy of Sciences（波兰科学院）；Max-Planck-Institut für Intelligente Systeme（马克斯·普朗克智能系统研究所）
In this paper, we investigate experimentally the non-equilibrium steady state of an active colloidal suspension under gravity field. The active particles are made of chemically powered colloids, showing self propulsion in the presence of an added fuel, here hydrogen peroxide. The active suspension is studied in a dedicated microfluidic device, made of permeable gel microstructures. Both the microdynamics of individual colloids and the global stationary state of the suspension under gravity - density profiles, number fluctuations - are measured with optical microscopy. This allows to connect th…
Magnetic nanoparticles in a colloidal solution self-assemble in various aligned structures, which has a profound influence on the flow behavior. However, the precise role of the microstructure in the development of the rheological response has not been reliably quantified. We investigate the self-assembly of dipolar colloids in simple shear using hybrid molecular dynamics and multi-particle collision dynamics simulations with explicit coarse-grained hydrodynamics; conduct simulated rheometric studies and apply micromechanical models to produce master curves, showing evidence of the universalit…
We present a quantitative confocal-microscopy study of the transient and final microstructure of particle-stabilised emulsions formed via demixing in a binary liquid. To this end, we have developed an image-analysis method that relies on structure factors obtained from discrete Fourier transforms of individual frames in confocal image sequences. Radially averaging the squared modulus of these Fourier transforms before peak fitting allows extraction of dominant length scales over the entire temperature range of the quench. Our procedure even yields information just after droplet nucleation, whe…
Specialized Monte Carlo simulation techniques and moment free energy method calculations, capable of treating fractionation exactly, are deployed to study the crystalline phase behaviour of an assembly of spherical particles described by a top-hat "parent" distribution of particle sizes. An increase in either the overall density or the degree of polydispersity is shown to generate a succession of phase transitions in which the system demixes into an ever greater number of face-centred cubic "daughter" phases. Each of these phases is strongly fractionated: it contains a much narrower distributi…
We show that two-dimensional bidisperse assemblies of colloids with strictly repulsive interactions exhibit stripe, cluster, and partially crystallized states when driven over a quenched random substrate. The nonequilibrium states on a substrate are significantly more ordered than equilibrium states both with and without substrates. A minimum substrate strength is necessary to induce the nonequilibrium pattern formation. Our results suggest that a combination of driving and quenched disorder offers a new approach to controlling pattern formation in colloid mixtures.
Starting from a generic model of a pore/bulk mixture equilibrium, we propose a novel method for modulating the composition of the confined fluid without having to modify the bulk state. To achieve this, two basic mechanisms - sensitivity of the pore filling to the bulk thermodynamic state and electric field effect - are combined. We show by Monte Carlo simulation that the composition can be controlled both in a continuous and in a jumpwise way. Near the bulk demixing instability, we demonstrate a field induced population inversion in the pore. The conditions for the realization of this method …
Strong effects of the Faraday instability on suspensions of rodlike colloidal particles are reported through measurements of the critical acceleration and of the surface wave amplitude. We show that the transition to parametrically excited surface waves displays discontinuous and hysteretic features. This subcritical behaviour is attributed to the shear-thinning properties of our colloidal suspensions thanks to a phenomenological model based on rheological data under large amplitude oscillatory shear. Birefringence measurements provide direct evidence that Faraday waves induce local nematic or…
Extreme deformation of soft matter is central to our understanding of the effects of shock, fracture, and phase change in a variety of systems. Yet, despite, the increasing interest in this area, far-from-equilibrium behaviours of soft matter remain challenging to probe. Colloidal suspensions are often used to visualise emergent behaviours in soft matter, as they offer precise control of interparticle interactions, and ease of visualisation by optical microscopy. However, previous studies have been limited to deformations that are orders of magnitude too slow to be representative of extreme de…
Non-equilibrium dynamics of topological defects can be used as a fundamental propulsion mechanism in microscopic active matter. Here, we demonstrate swimming of topological defect-propelled colloidal particles in (passive) nematic fluids through experiments and numerical simulations. Dynamic swim strokes of the topological defects are driven by colloidal rotation in an external magnetic field, causing periodic defect rearrangement which propels the particles. The swimming velocity is determined by the colloid's angular velocity, sense of rotation and defect polarity. By controlling them we can…
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 a…
Interactions between colloidal particles have hitherto usually been fixed by the suspension composition. Recent experimental developments now enable the control of interactions \emph{in-situ}. Here we use Brownian dynamics simulations to investigate the effect of controlling interactions on gelation, by "quenching" the system from an equilibrium fluid to a gel. We find that, contrary to the normal case of an instantaneous quench, where the local structure of the gel is highly disordered, controlled quenching results in a gel with a higher degree of local order. Under sufficiently slow quenchin…
We study how dispersions of colloidal particles in a cholesteric liquid crystal behave under a time-dependent electric field. By controlling the amplitude and shape of the applied field wave, we show that the system can be reproducibly driven out of equilibrium through different kinetic pathways and navigated through a glassy-like free energy landscape encompassing many competing metastable equilibria. Such states range from simple Saturn rings to complex structures featuring amorphous defect networks, or stacks of disclination loops. A non-equilibrium electric field can also trigger the align…
For applications of pulmonary surfactant delivery to the lungs, the question of rheology of the existing clinical formulations is of upmost importance. Recently, Ciutara and Zasadsinky (Soft Matter, 2021, 17, 5170-5182) measured the rheological properties of Infasurf, Survanta and Curosurf, three of the most used pulmonary surfactant substitutes. This study revealed that these fluids are shear-thinning and characterized by a yield stress. The results obtained by Ciutara et al. on Curosurf differ from our results published in Colloids and Surfaces B: Biointerfaces, 2019, 178, 337-345 and in ACS…
Appropriate combinations of laser beams can be used to trap and manipulate small particles with "optical tweezers" as well as to induce significant "optical binding" forces between particles. These interaction forces are usually strongly anisotropic depending on the interference landscape of the external fields. This is in contrast with the familiar isotropic, translationally invariant, van der Waals and, in general, Casimir-Lifshitz interactions between neutral bodies arising from random electromagnetic waves generated by equilibrium quantum and thermal fluctuations. Here we show, both theore…
While colloids are promising building blocks for the self-assembly of materials with novel microstructures, their numerous tunable parameters inhibit brute force searching for appropriate parameter combinations that yield self-assembly of a desired structure. Instead, inverse approaches that invoke a systematic optimization framework can effectively navigate this design space. In this proceeding, we apply one such inverse technique, Relative Entropy Minimization, to discover isotropic pairwise interaction potentials that prompt self-assembly of clusters in silico. The functional form of the pa…
Janus colloids propelled by light, e.g., thermophoretic particles, offer promising prospects as artificial microswimmers. However, their swimming behavior and its dependence on fluid properties and fluid-colloid interactions remain poorly understood. Here, we investigate the behavior of a thermophoretic Janus colloid in its own temperature gradient using numerical simulations. The dissipative particle dynamics method with energy conservation is used to investigate the behavior in non-ideal and ideal-gas like fluids for different fluid-colloid interactions, boundary conditions, and temperature-…
Synthetic hectorite clay Laponite RD/XLG is composed of disk-shaped nanoparticles that acquire dissimilar charges when suspended in an aqueous media. Owing to their property to spontaneously self-assemble, Laponite is used as a rheology modifier in a variety of commercial water-based products. Particularly, aqueous dispersion of Laponite undergoes liquid - to - solid transition at about 1 volume % concentration. The evolution of the physical properties as dispersion transforms to solid state is reminiscent of physical aging in molecular as well as colloidal glasses. The corresponding soft glas…
Self-assembly of colloidal particles due to elastic interactions in nematic liquid crystals promises tunable composite materials and can be guided by exploiting surface functionalization, geometric shape and topology, though these means of controlling self-assembly remain limited. Here, we realize low-symmetry achiral and chiral elastic colloids in the nematic liquid crystals using colloidal polygonal concave and convex prisms. We show that the controlled pinning of disclinations at the prisms edges alters the symmetry of director distortions around the prisms and their orientation with respec…
