Project description:We study the cluster structures of one-patch colloidal particles generated by droplet evaporation using Monte Carlo simulations. The addition of anisotropic patch-patch interaction between the colloids produces different cluster configurations. We find a well-defined category of sphere packing structures that minimize the second moment of mass distribution when the attractive surface coverage of the colloids χ is larger than 0 . 3 . For χ < 0 . 3 , the uniqueness of the packing structures is lost, and several different isomers are found. A further decrease of χ below 0 . 2 leads to formation of many isomeric structures with less dense packings. Our results could provide an explanation of the occurrence of uncommon cluster configurations in the literature observed experimentally through evaporation-driven assembly.
Project description:Emulsions are widely used in many industrial applications, and the development of efficient techniques for synthesizing them is a subject of ongoing research. Vapor condensation is a promising method for energy-efficient, high-throughput production of monodisperse nanoscale emulsions. However, previous studies using this technique are limited to producing small volumes of water-in-oil dispersions. In this work, a new method for the continuous synthesis of nanoscale emulsions (water-in-oil and oil-in-water) is presented by condensing vapor on free-flowing surfactant solutions. The viability of oil vaporization and condensation is demonstrated under mild heating/cooling using diverse esters, terpenes, aromatic hydrocarbons, and alkanes. By systematically investigating water vapor and oil vapor condensation dynamics on bulk liquid-surfactant solutions, a rich diversity of outcomes, including floating films, nanoscale drops, and hexagonally packed microdrops is uncovered. It is demonstrated that surfactant concentration impacts oil spreading, self-emulsification, and such behavior can aid in the emulsification of condensed oil drops. This work represents a critical step toward advancing the vapor condensation method's applications for emulsions and colloidal systems, with broad implications for various fields and the development of new emulsion-based products and industrial processes.
Project description:Particle shape is a critical parameter that plays an important role in self-assembly, for example, in designing targeted complex structures with desired properties. Over the last decades, an unprecedented range of monodisperse nanoparticle systems with control over the shape of the particles have become available. In contrast, the choice of micrometer-sized colloidal building blocks of particles with flat facets, that is, particles with polygonal shapes, is significantly more limited. This can be attributed to the fact that in contrast to nanoparticles, the larger colloids are significantly harder to synthesize as single crystals. It is now shown that a very simple building block, such as a micrometer-sized polymeric spherical colloidal particle, is already enough to fabricate particles with regularly placed flat facets, including completely polygonal shapes with sharp edges. As an illustration that the yields are high enough for further self-assembly studies, the formation of three-dimensional rotator phases of fluorescently labelled, micrometer-sized, and charged rhombic dodecahedron particles was demonstrated. This method for fabricating polyhedral particles opens a new avenue for designing new materials.
Project description:In this article, we report the synthesis and physical characterization of colloidal polystyrene particles that carry water-soluble supramolecular N,N',N″,-trialkyl-benzene-1,3,5-tricarboxamides (BTAs) on their surface. These molecules are known to assemble into one-dimensional supramolecular polymers via noncovalent interactions. By tethering the BTAs to charge-stabilized particles, the clustering behavior of the resulting colloids was dictated by a balance between interparticle electrostatic repulsion and the BTA-mediated attractions. Through careful tuning of the dispersing medium's ionic strength, a regime was found in which particle aggregation could be reversibly induced upon heating the dispersion. These findings clearly indicate that hydrophobic interactions, which become stronger upon heating, play an important role during the clustering process. Besides the thermoreversible nature of the generated hydrophobic interparticle attractions, we found the clustering to be selective, that is, the BTA-functionalized colloids do not interact with nonfunctionalized hydrophobic polystyrene particles. This selectivity in the association process can be rationalized by the preferred stacking of the surface-tethered BTAs. These selective intermolecular/particle bonds are likely stabilized by the formation of hydrogen bonds, as previously observed for analogous molecular BTA assemblies. The resulting driving force responsible for particle clustering is therefore dual in nature and depends on both hydrophobic attractions and hydrogen bonding.
Project description:In this study, we investigated the effect of the sulfur content in the NiCl2 precursor on the shape of nickel nanoparticles (Ni-NPs) prepared by chemical vapor synthesis. We obtained spherical Ni-NPs when using anhydrous NiCl2 mixed with NiSO4 or Na2SO4 with a molar ratio of 0.002 as precursors without changing any other process parameters whereas faceted Ni-NPs when using only anhydrous NiCl2 as a precursor. First-principles calculations supported experimental results, which showed that NiSO4-mixed NiCl2 and Na2SO4-mixed NiCl2 precursors favored the growth of spherical NPs.
Project description:A radiative vapor condenser sheds heat in the form of infrared radiation and cools itself to below the ambient air temperature to produce liquid water from vapor. This effect has been known for centuries, and is exploited by some insects to survive in dry deserts. Humans have also been using radiative condensation for dew collection. However, all existing radiative vapor condensers must operate during the nighttime. Here, we develop daytime radiative condensers that continue to operate 24 h a day. These daytime radiative condensers can produce water from vapor under direct sunlight, without active consumption of energy. Combined with traditional passive cooling via convection and conduction, radiative cooling can substantially increase the performance of passive vapor condensation, which can be used for passive water extraction and purification technologies.
Project description:Atomically precise metal nanoclusters (NCs) emerge as fascinating synthons in self-assembled materials. The self-assembly of metal NCs are highly sensitive to the environment because they have an inorganic-organic hybridized structure and a relatively complicated conformation. Here, it is shown that when confined in crowded colloids, a water-soluble Ag9 -cored nanocluster (Ag9 -NC) can self- assemble into ultra-long (up to millimeters) and photoluminescent ribbons with high flexibility. The ribbon contains rectangularly organized columns of Ag9 -NCs and can undergo secondary self-assembly to form bundled and branched structures. Formation of ribbons is observed in all the tested colloids, including lyotropic liquid crystals and disordered, three-dimensional network. The high viscosity/elasticity of the crowded colloids weakens gravity-induced sedimentation of the ribbons, leading to the formation of an interesting class of inorganic-organic composite materials where the hard Ag-containing skeleton strengthens the soft matter. The simultaneously occurring symmetry breaking during the self-assembly of Ag9 -NCs gives uncontrolled supramolecular chirality, which can be tuned through the majority rule and soldier-and-sergeant rule by the introduction of chiral seeds. The regulated chirality and the intrinsic photoluminescence of the Ag9 -NCs ribbons impart the composite material circularly polarized luminescence, opening the door for a variety of potential applications.
Project description:Model colloidal systems studied with confocal microscopy have led to numerous insights into the physics of condensed matter. Though confocal microscopy is an extremely powerful tool, it requires a careful choice and preparation of the colloid. Uncontrolled or unknown variations in the size, density, and composition of the individual particles and interactions between particles, often influenced by the synthetic route taken to form them, lead to difficulties in interpreting the behavior of the dispersion. Here we describe the straightforward synthesis of copolymer particles which can be refractive index- and density-matched simultaneously to a non-plasticizing mixture of high dielectric solvents. The interactions between particles are accurately tuned by surface grafting of polymer brushes using Atom Transfer Radical Polymerization (ATRP), from hard-sphere-like to long-ranged electrostatic repulsion or mixed charge attraction. We also modify the buoyant density of the particles by altering the copolymer ratio while maintaining their refractive index match to the suspending solution resulting in well controlled sedimentation. The tunability of the inter-particle interactions, the low volatility of the solvents, and the capacity to simultaneously match both the refractive index and density of the particles to the fluid opens up new possibilities for exploring the physics of colloidal systems.
Project description:Objects floating at a liquid interface, such as breakfast cereals floating in a bowl of milk or bubbles at the surface of a soft drink, clump together as a result of capillary attraction. This attraction arises from deformation of the liquid interface due to gravitational forces; these deformations cause excess surface area that can be reduced if the particles move closer together. For micrometer-sized colloids, however, the gravitational force is too small to produce significant interfacial deformations, so capillary forces between spherical colloids at a flat interface are negligible. Here, we show that this is different when the confining liquid interface has a finite curvature that is also anisotropic. In that case, the condition of constant contact angle along the three-phase contact line can only be satisfied when the interface is deformed. We present experiments and numerical calculations that demonstrate how this leads to quadrupolar capillary interactions between the particles, giving rise to organization into regular square lattices. We demonstrate that the strength of the governing anisotropic interactions can be rescaled with the deviatoric curvature alone, irrespective of the exact shape of the liquid interface. Our results suggest that anisotropic interactions can easily be induced between isotropic colloids through tailoring of the interfacial curvature.
Project description:The self-assembly of colloidal particles is a route to designed materials production that combines high flexibility, cost effectiveness, and the opportunity to create ordered structures at length scales ranging from nano- to micrometers. For many practical applications in electronics, photovoltaics, and biomimetic material synthesis, ordered mono- and bilayers are often needed. Here we present a novel and simple way to tune via external parameters the ordering of heterogeneously charged colloids into quasi two-dimensional structures. Depending on the charges of the underlying substrate and of the particles, a rich and versatile assembly scenario takes place, resulting from the complex interplay between directional attractive and repulsive particle-particle and particle-substrate interactions. Upon subtle variations of the relative charge of the system components, emerging via pH modification, reversible changes either from extended aggregates to a monomeric phase or from triangular to square domains are observed.