Formation Of Colloidal Crystals Research Articles

Modeling order–disorder boundaries of colloidal dispersions in organic solvents using interaction force measurements

HypothesisThe formation of soft colloidal crystals, which are nonclose-packed ordered arrays of colloidal particles suspended in a solvent, is dictated by a single physical factor that yields a fixed threshold at order–disorder boundaries for different experimental conditions such as ion concentration, solvent type, and particle size. Identifying the determinant factor and its threshold value should enable the prediction of the critical concentrations of colloidal particles to form soft colloidal crystals. ExperimentsSoft colloidal crystals were fabricated using a series of monohydric alcohols as dispersion media and reflectance spectra were measured to locate order–disorder boundaries. The interaction forces acting between particles were also measured by employing atomic force microscopy. FindingsThe interparticle forces at the order–disorder boundaries exhibited a universal threshold that was independent of the solvent types including alcohols and water. Therefore, the determinant factor for the formation of soft colloidal crystals was determined to be the force acting between the particles. Furthermore, a priori calculation of this critical force and consequently the critical particle concentration in colloidal systems was demonstrated by referring to the pressure at the liquid-to-solid transition in a hard sphere system (Alder transition).

PH‐Responsive Virus‐Based Colloidal Crystals for Advanced Material Platforms

AbstractBacteriophages have a well‐defined nanoscale size, shape, and surface chemistry, making them promising candidates for creating advanced biomaterials for applications including biocatalysis, drug delivery, and biosensing. This study demonstrates the self‐assembly of the ≈29 nm diameter bacteriophage Qbeta (Qubevirus durum) with the synthetic polycation, poly [2‐(methacryloyloxy)ethyl] trimethylammonium chloride (pMETAC), into compartmentalized colloidal crystals. The pH and the polymer chain length tune their self‐assembly and the resulting structure, with the potential for further chemical modification or loading with bioactive molecules. Small angle X‐ray scattering (SAXS), multi‐angle dynamic light scattering (DLS), and atomic force microscopy (AFM) are used for studying the Qbeta self‐assembly into the geometrically ordered aggregates. The suprastructures form at pH > 7.0 and disassemble at pH < 7.0. Zeta potential measurements and X‐ray photoelectron spectroscopy (XPS) show pMETAC adsorption onto the negatively charged Qbeta surface. The colloidal crystal formation is achieved without chemically modifying the Qbeta surface. Additionally, the Qbeta/pMETAC suprastructures can be easily separated from the suspension as macroscopic aggregate, maintaining their activity. Their simple preparation allows for large‐scale production of advanced materials in food and health science applications and nanotechnology. The insights from this study will further advance the tailored design and production of novel colloidal materials.

Formation of two-dimensional diamond-like colloidal crystals using layer-by-layer electrostatic self-assembly.

We report here that a two-dimensional (2D) diamond-like structure of micron-sized colloidal particles can be obtained by layer-by-layer self-assembly. Positively and negatively charged silica particles, 1 μm in diameter, were used in the experiments. On a positively charged, flat glass substrate, the first layer of negatively charged particles was prepared to form a non-close-packed 2D crystal. Then the second and third layers were fabricated using electrostatic adsorption. The positions of adsorbed particles were controllable by tuning the zeta-potential of the particles and the salt concentration of the medium. The FDTD calculations show that the 2D diamond structures of particles with higher refractive index (titania) have an absorption band in the wavelength range corresponding to the photonic band gap of the 3D bulk crystal. We expect these findings to be useful for the fabrication of novel photonic materials.

Numerical study of the effect of particle size dispersion on order within colloidal assemblies

The formation of colloidal crystals is of interest in many fields, especially because of their optical properties. These properties are dictated by the colloidal arrangement. It is known that introducing particles with different sizes can change the structure of crystals and thus their resultant optical properties. To better understand how specific arrangements of particles can be obtained, a detailed understanding of the formation mechanisms is needed. The influence of particle size distribution on the formation of colloidal crystals is studied by means of Brownian dynamics simulations performed with different types of interaction potentials. Crystal formation is first analyzed in systems containing homogeneous particles, then in systems with a size distribution.It is shown that the interaction potential has a strong influence on the colloidal arrangement. For homogeneous particles, the width of the potential well affects the aggregate shape: a larger width leads to more elongated structures. When a size distribution is introduced, aggregation becomes more difficult since the number of isolated colloids increases, and aggregates become disordered regardless of the interaction potentials. Depending on the interaction potential, differences in the aggregates are observed. These differences are rationalized in terms of the specific features of the different potentials.

Thermofluidic assembly of colloidal crystals

Colloidal crystals are interesting as functional structures due to their emergent photonic properties like photonic stop bands and bandgaps that can be used to redirect light. They are commonly formed by a drying process that is assisted by capillary forces at the drying fronts. In this manuscript, we demonstrate the optically induced dynamic thermofluidic assembly of 2D and 3D colloidal crystals. We quantify in experiment and simulation the structure formation and identify thermo-osmosis and temperature induced depletion interactions as the key contributors to the colloidal crystal formation. The non-equilibrium nature of the assembly of colloidal crystals and its dynamic control by laser-induced local heating promise new possibilities for a versatile formation of photonic structures inaccessible by equilibrium processes.

Formation and manipulation of 2D colloidal crystals driven by convective currents and electrostatic forces

Colloidal crystal plays a major role in novel optical devices such as waveguides, photonic crystals, and colloidal crystal lasers, among others. It has been known that colloidal crystals may self-assemble due to optical, electric, or chemical potentials, and light-induced thermal effects, such as thermophoresis and convective currents. In this work, the formation and manipulation of a self-limiting assembly of monolayer colloidal crystals using a 20 nm absorbing thin film of titanium and a CW-laser emitting at 1070 nm is reported. The colloidal particles, dragged by thermally induced convective currents, self-assembling over the titanium thin film around the laser focal spot. The self-assembled monolayer colloidal crystal tends to form a circular shape. Using numerical simulation, we obtained a potential well associated with the convective currents that spatially govern the radial extension of the monolayer colloidal crystal. We also show, that by changing the pH of the solution i.e., by tuning the electrostatic interaction, the monolayer colloidal crystal can be formed or destroyed. In addition, it was possible to create a larger monolayer colloidal structure covering an area of 600 μm2 using an array of six laser spots.

Beyond simple self-healing: How anisotropic nanogels adapt their shape to their environment.

The response of soft colloids to crowding depends sensitively on the particles' compressibility. Nanogel suspensions provide model systems that are often studied to better understand the properties of soft materials and complex fluids from the formation of colloidal crystals to the flow of viruses, blood, or platelet cells in the body. Large spherical nanogels, when embedded in a matrix of smaller nanogels, have the unique ability to spontaneously deswell to match their size to that of the nanogel composing the matrix. In contrast to hard colloids, this self-healing mechanism allows for crystal formation without giving rise to point defects or dislocations. Here, we show that anisotropic ellipsoidal nanogels adapt both their size and their shape depending on the nature of the particles composing the matrix in which they are embedded. Using small-angle neutron scattering with contrast variation, we show that ellipsoidal nanogels become spherical when embedded in a matrix of spherical nanogels. In contrast, the anisotropy of the ellipsoid is enhanced when they are embedded in a matrix of anisotropic nanogels. Our experimental data are supported by Monte Carlo simulations that reproduce the trend of decreasing aspect ratio of ellipsoidal nanogels with increasing crowding by a matrix of spherical nanogels.

Assembly Control at a Low Péclet Number in Ultracentrifugation for Uniformly Sized Nanoparticles

The intrinsic high diffusion rate of colloids at low Péclet number results in an extremely fast crystallization process and instant formation of colloidal crystals, even at an ultracentrifugal field of extremely high intensity. By introducing a small number of clusters in sedimention, it should be possible to slow down the crystallization process, thus making the assembly order tunable in preparative ultracentrifugation experiments. Here, we used sodium dodecyl sulfate-stabilized polystyrene nanoparticles (with a size dispersity of 1.07) dispersed in a solution of high ionic strength. Sedimentation and assembly of these nanoparticles were done using preparative ultracentrifugation at various angular velocities. The sedimentation process was also analyzed in situ by analytical ultracentrifugation in real time. By creating as low as 3% of clusters into these nearly uniformly sized polystyrene nanoparticle dispersions during the sedimentation process, the superstructure order becomes easily tunable between glassy and crystalline. Theoretical calculations complemented the experiments to explain the mechanism of cluster formation in sedimentation. This work provides a novel methodology to produce superstructures with a tunable packing order for colloids at low Péclet number.

Templating the morphology of soft microgel assemblies using a nanolithographic 3D-printed membrane

Filter cake formation is the predominant phenomenon limiting the filtration performance of membrane separation processes. However, the filter cake’s behavior at the particle scale, which determines its overall cake behavior, has only recently come into the focus of scientists, leaving open questions about its formation and filtration behavior. The present study contributes to the fundamental understanding of soft filter cakes by analyzing the influence of the porous membrane’s morphology on crystal formation and the compaction behavior of soft filter cakes under filtration conditions. Microfluidic chips with nanolithographic imprinted filter templates were used to trigger the formation of crystalline colloidal filter cakes formed by soft microgels. The soft filter cakes were observed via confocal laser scanning microscopy (CLSM) under dead-end filtration conditions. Colloidal crystal formation in the cake, as well as their compaction behavior, were analyzed by optical visualization and pressure data. For the first time, we show that exposing the soft cake to a crystalline filter template promotes the formation of colloidal crystallites and that soft cakes experience gradient compression during filtration.

Mechanochromic and Thermochromic Sensors Based on Graphene Infused Polymer Opals.

High quality opal‐like photonic crystals containing graphene are fabricated using evaporation‐driven self‐assembly of soft polymer colloids. A miniscule amount of pristine graphene within a colloidal crystal lattice results in the formation of colloidal crystals with a strong angle‐dependent structural color and a stop band that can be reversibly shifted across the visible spectrum. The crystals can be mechanically deformed or can reversibly change color as a function of their temperature, hence their sensitive mechanochromic and thermochromic response make them attractive candidates for a wide range of visual sensing applications. In particular, it is shown that the crystals are excellent candidates for visual strain sensors or integrated time‐temperature indicators which act over large temperature windows. Given the versatility of these crystals, this method represents a simple, inexpensive, and scalable approach to produce multifunctional graphene infused synthetic opals and opens up exciting applications for novel solution‐processable nanomaterial based photonics.

Front Cover: Autonomous Formation and Annealing of Colloidal Crystals Induced by Light‐Powered Oscillations of Active Particles (ChemSystemsChem 1/2020)

The Front Cover shows active Ag3PO4 nanoparticles herding bigger inactive SiO2 particles into colloidal crystals that exhibit oscillatory motion. The crystals disperse then rejoin/reorganize, undergoing “autonomous annealing”. More information can be found in the Communication by A. Altemose et al.

Autonomous Formation and Annealing of Colloidal Crystals Induced by Light‐Powered Oscillations of Active Particles

AbstractThe front cover artwork is provided by the Sen group at Penn State (USA). The image shows how active Ag3PO4 particles herd inactive SiO2 particles into colloidal crystals that exhibit oscillatory motion. The crystals disperse then rejoin/reorganize, undergoing “autonomous annealing”. Read the full text of the Communication at 10.1002/syst.201900021.

Temperature-Induced Coloration and Interface Shell Cross-Linking for the Preparation of Polymer-Based Opal Films.

The formation of colloidal crystals and their use as photonic materials are of high interest for various technologies in the field of sensing applications, as templates, absorber materials, catalysts, and membranes. In this study, core-shell particles consisting of a cross-linked poly(methyl methacrylate) core featuring a (polyacrylonitrile-co-styrene) shell are synthesized by starved-feed emulsion polymerization. The resulting particles are investigated with respect to size and monodispersity, as well as the core-to-shell ratio, by means of dynamic light scattering and transmission electron microscopy. Optimized particle sizes are 218 nm for the cores and 276 nm for the core-shell particles. For the formation of highly ordered and free-standing opal films, the particles are processed by the melt-shear organization technique. The resulting films show angle-dependent reflection colors, while reflected colors can be tailored by the design of the core-shell particles. As a focus of this work, polyacrylonitrile as part of the copolymer particle shell is advantageously used both for particle opal film stabilization and for tailoring the reflection colors of the opal films. It is shown that the cyclization reactions at the interface of the particles and within the matrix material significantly influence the optical properties of the opal films upon thermal treatment at 240 °C and for different heat holding times. For instance, the change of color can be simply set from red to blue upon defined thermal treatment conditions. Via this convenient protocol, brilliant reflection colors can thus be obtained based on the insights into the structure-property relationships of the underlying particle architectures and interface reactions. The scalable opal films will pave the way to functional colored materials as interesting candidates for a manifold of sensing applications and temperature-responsive polymeric materials.

Autonomous Formation and Annealing of Colloidal Crystals Induced by Light‐Powered Oscillations of Active Particles

AbstractSelf‐organization through communication is observed in many systems throughout nature, often resulting in a collective response to a change in the environment. Herein, we demonstrate a synthetic system that exhibits chemical communication between small active and larger inactive particles which drives the reversible assembly of the latter into colloidal crystals. Specifically, we report the autonomous hexagonal packing of inert silica particles due to the oscillatory behavior of neighboring silver phosphate micromotors under UV light in the presence of hydrogen peroxide. The colloidal crystals are formed under UV illumination and relax into a disordered state when the light is turned off. Furthermore, oscillatory waves generated by the active particles cause “autonomous annealing”, or elimination of defects between crystal boundaries of the silica colloidal crystals.

Large-Scale Self-Assembly in Weakly-Flocculated Suspensions

Background: Studies on the formation of colloidal crystals in concentrated suspensions have mainly been based on dispersed suspensions with a repulsive inter-particle potential of hard or nearly hard spheres. The self-assembly in weakly-flocculated suspensions has still been unrealized. Here, we report on the formation of ordered structures in concentrated suspensions of nearly-hard spherical particles with weakly-attractive inter-particle interactions that are an order of magnitude higher than the particles’ thermal energy. Methods: In our case, the self-assembly in such suspensions is not thermodynamically driven, but an external shear force must be applied. The driving force for the particles’ ordering is an increase in the inter-particle interactions. This manifests itself in a decrease in the average angle between the interparticle interaction direction and the applied shear stress direction. Results: For a successful ordering into a large-scale closed packed assembly, the external shear force must not exceed the inter-particle attractive interaction for the minimum possible average angle (as in the closed packed structures) but be high enough to enable the particles to move in the highly loaded suspension. Conclusion: The developed method for the self-assembly of the weakly flocculated systems can be applied very generally e.g. a control over a composition of heterogeneous colloidal crystals, manufacturing of the large-scale photonic crystals or preparation of very densely packed compacts of particles needed for the production of sintered ceramics.

Formation of colloidal crystals of maghemite nanoparticles: Experimental and theoretical investigations

Novel colloidal crystals made of maghemite nanocrystals are fabricated by a co-evaporation method with a mixture of ethanol/hexane. Through a series of comprehensive characterization performed by grazing incidence small-angle X-ray scattering (GISAXS) and field emission gun scanning electron microscope (FEG-SEM), we show the first example of well-defined face-centered cubic (fcc) colloidal crystals. In order to obtain a clear picture of the crystal formation, the amount of ethanol in the solution is monitored using gas chromatography. In parallel, the interactions between the nanocrystals are calculated by statistical mechanics theory using solubility parameters. Theory predicts the formation of colloidal crystals at quite high amounts of ethanol around 15%, in perfect agreement with experimental results. We show that the theory can further be applied to predict the optimal experimental conditions for the formation of colloidal crystals using other solvent mixtures.

Two-Component Fullerene Molecular Layers Assembled on the Au(111) Substrate

Self-assembly of binary and multicomponent colloidal crystals is an effective approach for the fabrication of structured new materials. The formation of colloidal crystals in most cases is controlled by optimized space occupation by the particles. C60 and C70 molecules, when treated as the smallest “colloidal particles”, can be used as model systems to study the formation of multicomponent molecular crystals in which the intermolecular forces are mainly of the van der Waals type. By deposition of C60 and C70 molecules onto Au(111), the mixing of the two molecules has been investigated. Both C60 and C70 form close-packed layers on Au(111), but with different lattice constants. At room temperature, the molecules within the molecular layer have complete freedom to rotate. The boundary between the C60 and the C70 domains consists of row dislocations. Adding C60 onto a C70 layer has an interesting effect in that C60 molecules can push their way into the C70 layer and force the C70 molecules to take a fixed upright configuration where the long axis of the molecule is perpendicular to the interface. Significant interlayer diffusion takes place at elevated temperatures. When C70 is added to a C60 layer, there is little evidence of C70 getting into the C60 layer. The second layer C70 forms a lattice-matched structure by taking the upright orientation.

Formation of three-dimensional colloidal crystals in a nematic liquid crystal.

We investigate the possible structures of three-dimensional colloidal crystals formed when these spherical particles are dispersed in a liquid crystal. The case of a strong homeotropic boundary condition is considered here. Their corresponding defect structures in the space-filler nematic liquid crystal are induced by the presence of the spherical surface of the colloids and produce an attraction between colloidal particles. Here, a standard Landau-de Gennes free energy model for a spatially inhomogeneous liquid crystal is numerically minimized to yield an optimal configuration of both spherical colloids and the orientational field. The stable and metastable structures obtained in this work are described and analyzed according to the type of periodic liquid-crystal defect lines that couple the colloidal spheres together. A large range of the spherical size is covered in this study, corresponding to a 5CB-liquid-crystal comparison for assembling micron- to nano-sized colloidal spheres. Multiple configurations are found for each given particle size and the most stable state is determined by a comparison of the free energies. From large to small colloidal particles, a sequence of structures, which range from quasi-one-dimensional (columnar), to quasi-two-dimensional (planar), and to truly three-dimensional, are found to exist.

Semisoft Colloidal Crystals in Ionic Liquids.

Here, we introduce a technique for the direct formation of semisoft colloidal crystals of hybrid particles in nonvolatile ionic liquid (IL) solvents. The hybrid particles are comprised of a silica core and a densely grafted polymer brush shell, which were synthesized by surface-initiated living radical polymerization. A phase transition of the suspensions from a disordered fluid to a crystallized system was observed within a narrow concentration range. Confocal laser scanning microscopy observation and ultraviolet-visible light (UV-vis) spectrometry confirmed the highly ordered structure of the hybrid particles in ionic liquids. The effect of the hybrid particle structure on the photonic band gap of the colloidal crystals was investigated, and the band gaps varied by changing graft chain lengths. In addition, the colloidal crystal suspensions were successfully immobilized in ILs.

Single-source macroporous hybrid materials by melt-shear organization of core–shell particles

The preparation of porous materials is an interesting field for a huge variety of potential applications. Herein we report an efficient and convenient strategy for the creation of inverse colloidal crystal structures based on soft core/shell polymer particle templating. This single-source strategy is based on starved-feed emulsion polymerization of hybrid core/shell particles consisting of a poly(methyl methacrylate-co-allyl methacrylate) (P(MMA-co-ALMA)) core and a poly(ethyl acrylate-co-(3-methacryloxypropyl-trimethoxysilane)) (PEA-co-PMEMO) shell. The resulting monodisperse particles are analyzed with respect to their size and distribution by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. The hybrid monodisperse core/shell particles can be aligned to a colloidal crystal by using the convenient melt-shear organization technique. As a result, free-standing and crack-free hybrid polymer colloidal crystal films are accessible without the need of any solvent or dispersion medium. The processing step is investigated regarding different parameters comprising temperature and pressure for the influence on the colloidal crystal film formation. Furthermore, resulting core/shell ratio is tailored by starved-feed emulsion polymerization conditions, since the ratio affects the quality of the porous structure after thermal treatment of colloidal crystal films. The incorporation of alkoxysilane-containing monomers offers a unique crosslinking strategy that yields mechanically robust and thermally stable films. Due to the increased stability, a removal of PMMA cores is possible by thermal treatment of the templating colloidal crystal films leading to almost isoporous free-standing hybrid materials as determined by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM).