Monolayer Of Particles Research Articles

Method of Absorbing Material Formation Based on Magnetically Controlled Particles of Fe3O4

A method of formation of three-dimensional arrays of magnetically controlled particles from iron oxide Fe3O4 using a rotating permanent magnetic field is developed to create a material that absorbs electromagnetic radiation in the microwave range. The use of laboratory setup with a rotating magnetic field of permanent magnets makes it possible to obtain a composite with a close packing of particles, in which the principle of self-organization of monolayers of magnetic particles is realized. The reflection spectra, absorption spectra, and attenuation spectra of the electromagnetic radiation of composites with a three-dimensional array of close-packed magnetic particles of Fe3O4 with a thickness of 3 mm and 6 mm consisting of 15 and 30 flat monolayers of particles, respectively, are obtained. The technique for three-dimensional arrays of magnetic particles of Fe3O4 and the laboratory setup for its implementation are promising to produce composite materials using a wide range of microparticles and nanoparticles.

Shear dynamics of confined bijels

Bicontinuous interfacially jammed emulsion gels (“bijels”) represent a new class of soft materials made of a densely packed monolayer of solid particles sequestered at the interface of a bicontinuous fluid. Their mechanical properties are relevant to many applications, such as catalysis, energy conversion, soft robotics, and scaffolds for tissue engineering. While their stationary bulk properties have been covered in depth, much less is known about their behavior in the presence of an external shear. In this paper, we numerically study the dynamics of a bijel confined within a three-dimensional rectangular domain and subject to a symmetric shear flow sufficiently intense to break the material. Extensive numerical simulations reveal that the shear flow generally promotes the detachment of a sizable amount of particles from the fluid interface and their accumulation in the bulk. Fluid interfaces undergo large stretching and deformations along the flow direction, an effect that reduces their capability of entrapping particles. These results are supported by a series of quantitative indicators such as (i) curvature of the fluid interface, (ii) spatial distribution of the colloidal particles, and (iii) fluid flow structure within the microchannel.

Particle monolayer assembly in evaporating salty colloidal droplets

Ring-shaped deposits can be often found after a droplet evaporates on a substrate. If the fluid in the droplet is a pure liquid and its contact line remains pinned during the process, the mechanism behind such ring-shaped deposition is the well-known coffee-stain effect. However, adding small amounts of salt to such a droplet can change the internal flow dramatically and consequently change the deposition mechanism. Due to an increase of surface tension in the contact line region, a Marangoni flow arises which is directed from the apex of the droplet towards the contact line. As a result, particles arrive at the contact line following the liquid-air interface of the droplet. Interestingly, the deposit is also ring-shaped, as in the classical coffee-stain effect, but with a radically different morphology: particles form a monolayer along the liquid-air interface of the droplet, instead of a compact three-dimensional deposit. Using confocal microscopy, we study particle-per-particle how the assembly of the colloidal monolayer occurs during the evaporation of droplets for different initial concentration of sodium chloride and initial particle dilution. Our results are compared with classical diffusion-limited deposition models and open up an interesting scenario of deposits via interfacial particle assembly, which can easily yield homogeneous depositions by manipulating the initial salt and particle concentration in the droplet.

Scattering and Absorption of Light by a Monolayer of Spherical Particles under Oblique Illumination

The problem of light scattering and absorption by a monolayer of homogeneous spherical particles at an arbitrary angle of incidence of a plane wave, which determines the phase shift between the averaged fields in the particles, has been solved. The solution is based on the quasi-crystalline approximation of the theory of multiple scattering of waves, the mean-field approximation, and the multipole expansion of the fields and the tensor Green function in terms of vector spherical wave functions. Formulas for determining the angular distribution of the incoherently scattered field intensity, the incoherent scattering, absorption, coherent transmission, and reflection coefficients have been derived. The dependences of these characteristics on the direction of illumination are illustrated using partially ordered monolayers of dielectric and semiconductor particles as an example. It is shown that: (i) under oblique illumination the angular distribution of the scattered radiation in azimuthal scattering angle for any polarization of the incident wave (except for p and s) is asymmetric relative to the plane of incidence, (ii) the maximum of the angular distribution of the radiation transmitted through the monolayer can approach its normal with increasing angle of incidence and/or concentration of particles, (iii) there exist conditions under which the bulk of the scattered radiation is concentrated in the direction opposite to the direction of the incident radiation, and (iv) the dependence of the monolayer absorption coefficient on the illumination angle has extrema whose positions and magnitudes are determined by the polarization of the incident wave.

Analysis of soft and hard nanoparticle alternating multilayers for the development of theory for long-period stacking order structure prepared by Langmuir-Blodgett method

Two types of hard and soft nanoparticles with a size of 5 nm were alternately layered to adjust the multi-particle structure with high regularity, and structural analysis was performed. Specifically, we alternately transferred two kinds of single-particle layers composed of surfactant-modified organo-magnetite and a hydrophobic polymer to a solid substrate using the Langmuir-Blodget (LB) method. The morphology of two-dimensional particle integration in each single particle layer was confirmed by atomic force microscopy observations. The obtained LB multilayers exhibited almost the same periodicity, crystallite size, and lattice distortion, based on X-ray diffraction (XRD) analysis. The alternating multilayers composed of hard and soft particle monolayers were not inferior to single component multilayers in terms of periodicity and regularity. The utilization of this preparation method facilitates effective control of the period of hard and soft layers. It is asserted that the high degree of regularity was attained due to the affinity and miscibility between the organic polymer particle layer and the modified organic chains on the inorganic nanoparticle surface. The most notable result is that in the XRD data, the spacing between inorganic nanoparticles was not enhanced, and the period of the hard-soft particle correlation was confirmed. Therefore, it seems that both layers have the same high degree of regularity.

Mechanical Stimulation of Adhesion Receptors Using Light-Responsive Nanoparticle Actuators Enhances Myogenesis.

The application of cyclic strain is known to enhance myoblast differentiation and muscle growth in vitro and in vivo. However, current techniques apply strain to full tissues or cell monolayers, making it difficult to evaluate whether mechanical stimulation at the subcellular or single-cell scales would drive myoblast differentiation. Here, we report the use of optomechanical actuator (OMA) particles, comprised of a ∼0.6 μm responsive hydrogel coating a gold nanorod (100 × 20 nm) core, to mechanically stimulate the integrin receptors in myoblasts. When illuminated with near-infrared (NIR) light, OMA nanoparticles rapidly collapse, exerting mechanical forces to cell receptors bound to immobilized particles. Using a pulsed illumination pattern, we applied cyclic integrin forces to C2C12 myoblasts cultured on a monolayer of OMA particles and then measured the cellular response. We found that 20 min of OMA actuation resulted in cellular elongation in the direction of the stimulus and enhancement of nuclear YAP1 accumulation, an effector of ERK phosphorylation. Cellular response was dependent on direct conjugation of RGD peptides to the OMA particles. Repeated OMA mechanical stimulation for 5 days led to enhanced myogenesis as quantified using cell alignment, fusion, and sarcomeric myosin expression in myotubes. OMA-mediated myogenesis was sensitive to the geometry of stimulation but not to MEK1/2 inhibition. Finally, we found that OMA stimulation in regions proximal to the nucleus resulted in localization of the transcription activator YAP-1 to the nucleus, further suggesting the role of YAP1 in mechanotransduction in C2C12 cells. These findings demonstrate OMAs as a novel tool for studying the role of spatially localized forces in influencing myogenesis.

Sequential Selective Solvent On-Film Annealing: Fabrication of Monolayers of Ordered Anisotropic Polymer Particles.

Although various strategies have been developed to prepare anisotropic polymeric particles, it remains challenging to fabricate monolayers of anisotropic polymeric particles, which can extend the applications of anisotropic particles. Here, we develop a novel and facile approach to fabricate monolayers of anisotropic polymeric particles. Monolayers of polystyrene (PS) microspheres with a mean diameter of 10 μm are deposited on glass substrates coated with poly(methyl methacrylate) films, followed by sequential selective solvent on-film annealing processes. Monolayers of anisotropic polymeric particles, such as the snowman-like PS particles, are successfully fabricated. Such unique structures possess the long-range ordering of monolayers (the structure factor) and the anisotropic geometry of individual particles (the form factor). The nanomechanical properties of the PS particles are also characterized using atomic force microscopy force volume measurements, showing a decrease in the Young's moduli of the PS particles owing to the looser packing of the polymer chains. This work provides the most facile and versatile strategy by far to fabricate monolayers of ordered anisotropic polymeric particles, which are inaccessible by other traditional means.

Hydrophilic Coating of Copper Particle Monolayer Wicks for Enhanced Passive Water Transport

Passive water transport through thin-surface wicks made of heat conducting material is important for developing thermal management devices such as heat pipes and spreaders. In this study, we demonstrated the hydrophilic coating of a Cu particle monolayer wick for enhanced water transport. We fabricated a Cu particle monolayer using Cu powder with a nominal particle diameter of 100 μm and determined the particle size distribution using scanning electron microscopy (SEM). We observed a remarkable change in the water contact angle on the application of a hydrophilic coating, which demonstrated the enhanced passive water transport. The elemental mapping of Cu, O, and Si obtained by electron probe microanalysis confirmed the deposition of the SiO2-based coating material on each Cu particle. Although the Cu particles were only partially covered by SiO2, a remarkable enhancement in wettability was achieved. Finally, we conducted a rate-of-rise experiment to quantitatively characterize the water transport performance of the coated Cu particle monolayer. Thus, we propose hydrophilic coating as a simple and effective method to enhance passive water transport through Cu particle monolayer wicks.

Spatial Segregation of Microspheres by Rubbing-Induced Triboelectrification on Patterned Surfaces.

Particle (monolayer) assembly is essential to various scientific and industrial applications, such as the fabrication of photonic crystals, optical sensors, and surface coatings. Several methods, including rubbing, have been developed for this purpose. Here, we report on the serendipitous observation that microparticles preferentially partition onto the fluorocarbon-coated parts of patterned silicon and borosilicate glass wafers when rubbed with poly(dimethylsiloxane) slabs. To explore the extent of this effect, we varied the geometry of the pattern, the substrate material, the ambient humidity, and the material and size of the particles. Partitioning coefficients amounted up to a factor of 12 on silicon wafers and even ran in the 100s on borosilicate glass wafers at zero humidity. Using Kelvin probe force microscopy, the observations can be explained by triboelectrification, inducing a strong electrostatic attraction between the particles and the fluorocarbon zones, while the interaction with the noncoated zones is insignificant or even weakly repulsive.

Morphological Control of Linear Particle Deposits from the Drying of Inkjet-Printed Rivulets.

We studied the morphology of linear particle deposits obtained by inkjet printing of a silica nanoparticle suspension in drying conditions where contact line depinning occurs. We show that this evaporation mode can be obtained by adjusting the particle concentration in different solvents. For isolated drops, deposited manually or by inkjet printing, drying induces the formation of two concentric rings in which particles self-assemble into a monolayer. For fused drops, our main result is that stable rivulets could be formed by drop overlap leading, after drying, to the formation of three parallel lines composed of a self-assembled particle monolayer. The three lines are of homogeneous thickness with two very thin outer lines (∼1 μm width) and a wider central line (∼20 μm width). We reveal how the width of the resulting lines is influenced by drop spacing in a predictable manner for a large experimental window knowing the drop size.

Sampling and Mass Detection of a Countable Number of Microparticles Using on-Cantilever Imprinting.

Liquid-borne particles sampling and cantilever-based mass detection are widely applied in many industrial and scientific fields e.g., in the detection of physical, chemical, and biological particles, and disease diagnostics, etc. Microscopic analysis of particles-adsorbed cantilever-samples can provide a good basis for measurement comparison. However, when a particles-laden droplet on a solid surface is vaporized, a cluster-ring deposit is often yielded which makes particles counting difficult or impractical. Nevertheless, in this study, we present an approach, i.e., on-cantilever particles imprinting, which effectively defies such odds to sample and deposit countable single particles on a sensing surface. Initially, we designed and fabricated a triangular microcantilever sensor whose mass m0, total beam-length L, and clamped-end beam-width w are equivalent to that of a rectangular/normal cantilever but with a higher resonant frequency (271 kHz), enhanced sensitivity (0.13 Hz/pg), and quality factor (~3000). To imprint particles on these cantilever sensors, various calibrated stainless steel dispensing tips were utilized to pioneer this study by dipping and retracting each tip from a small particle-laden droplet (resting on a hydrophobic n-type silicon substrate), followed by tip-sensor-contact (at a target point on the sensing area) to detach the solution (from the tip) and adsorb the particles, and ultimately determine the particles mass concentration. Upon imprinting/adsorbing the particles on the sensor, resonant frequency response measurements were made to determine the mass (or number of particles). A minimum detectable mass of ~0.05 pg was demonstrated. To further validate and compare such results, cantilever samples (containing adsorbed particles) were imaged by scanning electron microscopy (SEM) to determine the number of particles through counting (from which, the lowest count of about 11 magnetic polystyrene particles was obtained). The practicality of particle counting was essentially due to monolayer particle arrangement on the sensing surface. Moreover, in this work, the main measurement process influences are also explicitly examined.

Coalescence Dynamics of Particle-Laden Bubbles

Understanding the coalescence of particle-laden bubbles is crucial to our understanding of the role of particles in stabilizing liquid foams. In this work, the coalescence of microparticle-laden bubbles is studied experimentally using high-speed photography. In particular, the interparticle forces in the neck region during the early stage of bubble coalescence are calculated. The results indicate that a monolayer of silica particles coating the bubble surfaces hinders the growth dynamics of the air neck formed between the coalescing bubbles. We postulate that the decrease in the growth dynamics is due to the surface pressure caused by the particle interaction after the initiation of bubble coalescence. We identify that the apparent surface tension in the neck region increases with time for particle-laden bubbles and is lower for larger particle sizes. These findings enhance our understanding of the role of particles on the dynamics of fast deforming interfaces.

Particle Monolayer-Stabilized Light-Sensitive Liquid Marbles from Polypyrrole-Coated Microparticles

Liquid marbles are water droplets coated with solid particles that prevent coalescence and allow storage, transport, and handling of liquids in the form of a powder. Here, we report on the formation of liquid marbles that are stabilized entirely by a single monolayer of solid particles and thus minimize the amount of required solid material. As stabilizing particles, we synthesize relatively-monodisperse, 80 m-sized polystyrene (PS) particles coated with heptadecafluorooctanesulfonic acid-doped polypyrrole (PPy-C8F) shell (PS/PPy-C8F particles) by aqueous chemical oxidative seeded polymerization of pyrrole using FeCl3 as an oxidant and heptadecafluorooctanesulfonic acid as a hydrophobic dopant. We characterize the physicochemical properties of the particles as a function of the PPy-C8F loading. Laser diffraction particle size analyses of dilute aqueous suspensions indicate that the polymer particles disperse stably in water medium before and after coating with the PPy-C8F shell. X-ray photoelectron spectroscopy studies indicate the formation of a PPy-C8F shell around the PS seed particles, which was further supported by a deflated morphologies observed by scanning electron microscopy after extraction of the PS component from the PS/PPy-C8F particles. We investigate the capabilities of the dried PS/PPy-C8F particles to act as a liquid marble stabilizer. Stereo- and laser microscope observations, as well as gravimetric studies, confirm that the PS/PPy-C8F particles adsorb to the water droplet surface in the form of a particle monolayer with the characteristic hexagonal close-packed structure expected for spherical (colloidal) particles. Mechanical integrity of the liquid marble increases with an increase of PPy-C8F loading of the PS/PPy-C8F particles. The water contact angle of the PS/PPy-C8F particles at air-water interface increases from 82±12º to 102±17º with an increase of PPy-C8F loading. This increase in water contact angle directly correlates with the shape of the LM, with higher contact angles giving more spherical LMs. Furthermore, the broadband light absorption properties of the PPy coating was used to control evaporation rate of the enclosed water phase on demand by irradiation with a near infrared laser. The evaporation rate could be finely controlled by the thickness of the PPy-C8F shell of the particles stabilizing the liquid marbles.

Temperature and electrostatics effects on charged poly(N-isopropylacrylamide) microgels at the interface

Thermoresponsive microgels based on poly-N-isopropylacrylamide (PNIPAM) have many biomedical applications owing to their biocompatibility and their Volume Phase Transition Temperature (VPTT) around the physiological temperature. Understanding the surface structure of PNIPAM microgels in monolayers is important in terms of fundamental science and towards their use in thermoresponsive emulsions. However, to date there are no reported studies of PNIPAM monolayers above and below the VPTT. In addition, the role of electrostatics in surface films of charged microgels remains controversial. Hence, in the present paper, we study the surface conformation of charged PNIPAM at different swelling states. Shrunken PNIPAM microgels in bulk show higher effective charge than swollen microgels. In agreement with this, we find that monolayers of shrunken PNIPAM particles are compressed more easily than that of swollen PNIPAM particles. The role of electrostatic interactions is further addressed by modifying the concentration of electrolyte, which alters the effective charge but retains the particle size of microgels. We find that screening the effective charge of the microgel has a strong impact on the lateral packing of the monolayer displacing the compression isotherms to higher normalised areas. Moreover, the displacement correlates with the changes in the effective charge of the microgels induced by the electrolyte. Hence, we prove that beyond the different swelling ratio, electrostatics can modulate the interactions between charged microgel particles at the interface.

Decimating Spatial Frequency Components in Periodically Modulated Nanoscale Surface Structures for Sensing of Ambient Refractive Index Changes.

In our previous study, we developed an array of unique porous structures (an array of barnacle-like porous structures) to apply to biosensing chips. The porous structure was formed by an internal swelling phenomenon of a polystyrene colloidal particle monolayer, which was surrounded by a poly(vinyl alcohol) layer, for the duration of the monolayer’s immersion in a toluene bath. Barnacle-like porous structures were formed when polystyrene particles that had rapidly swelled broke the outer layer around the top of the particles. However, after the surface was coated with a thin Ag layer, the porous structure showed a relatively broad extinction spectrum that was undesirable for sensing chips based on both surface plasmon extinction and grating coupling. In this paper, we propose an approach to obtain relatively sharp extinction spectra based on the decimation of the spatial frequencies of the porous structures. This study also investigates formation properties in more detail to control the structural features of the resultant porous structures. A relatively sharp peak in the extinction spectrum was ultimately obtained.

Collective Directional Locking of Colloidal Monolayers on a Periodic Substrate.

We investigate the directional locking effects that arise when a monolayer of paramagnetic colloidal particles is driven across a triangular lattice of magnetic bubbles. We use an external rotating magnetic field to generate a two-dimensional traveling wave ratchet forcing the transport of particles along a direction that intersects two crystallographic axes of the lattice. We find that, while single particles show no preferred direction, collective effects induce transversal current and directional locking at high density via a spontaneous symmetry breaking. The colloidal current may be polarized via an additional bias field that makes one transport direction energetically preferred.

Hydrodynamic Solvent Coupling Effects in Quartz Crystal Microbalance Measurements of Nanoparticle Deposition Kinetics.

Hydrodynamic coupling effects pertinent to quartz crystal microbalance (QCM) investigation of nanoparticle adsorption kinetics were evaluated using atomic force microscopy and the theoretical modeling. Monodisperse polymer particles of the size between 26 and 140 nm and the density of 1.05 g cm–3 were used. The ζ-potential of particles was opposite to the substrate ζ-potential that promoted their irreversible adsorption on the silica sensor. The experimental kinetic data were interpreted in terms of theoretical calculations derived from the hybrid random sequential adsorption model. This allowed us to determine the amount of hydrodynamically coupled solvent (electrolyte) for the absolute particle coverage range up to 0.5. The coupling function representing the ratio of the solvent to the particle volumes was also determined and used to explicitly calculate the solvent level in particle monolayers. It is shown that the solvent level abruptly increases with the particle coverage attaining values comparable with the particle size. One can expect that these results can serve as useful reference data for the interpretation of protein adsorption kinetics on rough surfaces where the presence of stagnant solvent is inevitable.

Inhomogeneity of Structural and Dynamical Characteristics of Dusty Plasma in a Gas Discharge

Dusty plasma crystals are commonly considered as spatially homogeneous structures with equal values of their structural and thermodynamic parameters in various regions of the system. Inhomogeneity of the interparticle distance, the amplitude of thermal particle oscillations, the Lindemann parameter, and the coupling parameter is shown to arise even in a system of particles with a simplified interaction model including a screened Coulomb potential and a parabolic trap. The kinetic energy distribution for particles in an inhomogeneous dusty plasma monolayer is investigated: it is shown that the mean kinetic energy of particles in the central part of the structure can differ significantly from the mean kinetic energy of particles on its periphery due to the inhomogeneity of structural parameters. The detected effects are verified using analytical methods and numerical simulations and by comparison with a dusty plasma experiment in a dc glow discharge. The results obtained are of great importance for investigating finite systems of like charges in a trap and studying the mechanism of phase transitions in dusty plasma systems.

Packing density, homogeneity, and regularity: Quantitative correlations between topology and thermoresponsive morphology of PNIPAM-co-PAA microgel coatings

This study investigates the formation of monolayers of microgel particles comprising poly[(N-isopropylacrylamide)-co-(acrylic acid)] on solid substrates, their surface morphology, and stimuli-responsiveness. Crosslinked microgels with different chemical composition were produced to show a broad range of responses in hydrodynamic radius and degree of self-assembly with temperature and pH. Microgels were deposited on silicon wafers primed with a bilayer of poly(octadecene-alt-maleic anhydride) and polyethyleneimine by either incubation or spin coating of aqueous suspension of microgels at different temperature and pH. The characterization of the microgel-coated wafers led to the identification of three metrics describing microgel arrangement: density (ρ); heterogeneity (H), which correlates strongly with ρ and depends on deposition temperature and pH with statistical significance, but not on microgel composition; and packing efficiency (PE), which portrays the regularity of microgel arrangement and exhibits no correlation with ρ nor H. The values of ρ, H, and PE calculated for in silico models of microgel coatings confirmed that these three metrics portray distinct characteristics of surface topology. Finally, profilometry analysis showed that microgel coatings respond to thermal stimuli with sensible variations in surface roughness; notably, the thermal variation of roughness correlates strongly with ρ and H, and to a lesser extent with PE.

Interference Provides Clarity: Direct Observation of 2D Materials at Fluid-Fluid Interfaces.

Monolayer particles of two-dimensional (2D) materials represent a scientifically and technologically interesting class of anisotropic particles with colloidal-scale lateral sizes but sub-nanometer thicknesses. This atomic-scale thickness leads to interesting phenomena that can be exploited in next-generation thin-film technologies, and fluid-fluid interfaces provide a potentially scalable platform to confine, assemble, and deposit functional thin films of 2D materials. However, directly observing how these materials interact and assemble into a given film morphology is experimentally challenging because of their sub-nanometer thicknesses. Here, we demonstrate the ability to directly observe graphene, molybdenum disulfide (MoS2), and hexagonal boron nitride (h-BN) particles at fluid-fluid interfaces using interference reflection microscopy (IRM). Monolayer MoS2 and graphene particles demonstrated >10% optical contrast at an air-water interface, which allowed us to quantitatively analyze in situ images of self-assembled MoS2 particles and to map trajectories of interacting graphene particles. Additionally, the Brownian motion of a graphene particle was tracked and analyzed in the context of passive microrheology theory for 2D particle probes. Our results demonstrate how IRM can be used to obtain quantitative spatiotemporal information regarding the self-assembly and dynamics of 2D materials at fluid-fluid interfaces. It will have a significant impact on our ability to investigate systems of atomically thin particles at fluid-fluid interfaces, an area that has fundamental scientific importance and materials science applications but has suffered from a lack of direct, in situ observation techniques.