Shape Anisotropy Of Particles Research Articles

Nano-sized SnO2: Planar defects or particle shape anisotropy?

Nano-sized SnO2: Planar defects or particle shape anisotropy?

Design and batch fabrication of anisotropic microparticles toward small-scale robots using microfluidics: recent advances.

Small-scale robots with shape anisotropy have garnered significant scientific interest due to their enhanced mobility and precise control in recent years. Traditionally, these miniature robots are manufactured using established techniques such as molding, 3D printing, and microfabrication. However, the advent of microfluidics in recent years has emerged as a promising manufacturing technology, capitalizing on the precise and dynamic manipulation of fluids at the microscale to fabricate various complex-shaped anisotropic particles. This offers a versatile and controlled platform, enabling the efficient fabrication of small-scale robots with tailored morphologies and advanced functionalities from the microfluidic-derived anisotropic microparticles at high throughput. This review highlights the recent advances in the microfluidic fabrication of anisotropic microparticles and their potential applications in small-scale robots. In this review, the term 'small-scale robots' broadly encompasses micromotors endowed with capabilities for locomotion and manipulation. Firstly, the fundamental strategies for liquid template formation and the methodologies for generating anisotropic microparticles within the microfluidic system are briefly introduced. Subsequently, the functionality of shape-anisotropic particles in forming components for small-scale robots and actuation mechanisms are emphasized. Attention is then directed towards the diverse applications of these microparticle-derived microrobots in a variety of fields, including pollution remediation, cell microcarriers, drug delivery, and biofilm eradication. Finally, we discuss future directions for the fabrication and development of miniature robots from microfluidics, shedding light on the evolving landscape of this field.

Meso-scale investigation on the permeability of frozen soils with the lattice Boltzmann method

Complex composition and intricate pore-scale structure of frozen soils poses significant challenges in reliably and efficiently obtaining their permeability. In this study, we propose a modified quartet structure generation set (QSGS) numerical tool for generating frozen soils and present the development of a computational simulation code based on the multiple-relaxation-time lattice Boltzmann method (LBM). In the modified QSGS, the arc-shaped water-ice interface is depicted, and the influence of pore-scale geometry on freezing temperature is considered. The validity of combining the proposed QSGS model and the LBM code is proved by comparing calculated results to analytical and experimental results of porous media. Our objective was to investigate the effects of soil features, including porosity, grain diameter, shape anisotropy of soil particles, and ice content on the intrinsic permeability of frozen soil. Additionally, we examined the relationship between these features and the specific surface area and tortuosity. Numerical results show that the intrinsic permeability of frozen soils increases with increasing porosity, larger granular diameter, and anisotropy, which is identical with the pressure gradient. The presence of ice led to clogging flow pathways and drastically decreased the intrinsic permeability, which is significantly less than unfrozen soil with same effective porosity. This study provides a useful tool to investigate the intricate interplay between the pore-scale structure and the intrinsic permeability of frozen soils.

The Paradoxical Behavior of Rough Colloids at Fluid Interfaces.

Colloidal particles adsorb and remain trapped at immiscible fluid interfaces due to strong interfacial adsorption energy with a contact angle defined by the chemistry of the particle and fluid phases. An undulated contact line may appear due to either particle surface roughness or shape anisotropy, which results in a quadrupolar interfacial deformation and strong long-range capillary interaction between neighboring particles. While each effect has been observed separately, here we report the paradoxical impact of surface roughness on spherical and anisotropic ellipsoidal polymer colloids. Using a seeded emulsion polymerization technique, we synthesize spherical and ellipsoidal particles with controlled roughness magnitudes and topography (convex/concave). Via in situ measurement of the interfacial deformation around colloids at an air-water interface, we find that while surface roughness strengthens the quadrupolar deformation in spheres as expected by theory, in stark contrast, it weakens the same in ellipsoids. As roughness increases, particles of both shapes become more hydrophilic, and their apparent contact angle decreases. Using numerical predictions, we show that this partially explains the decreased interfacial deformation and capillary interactions between the ellipsoids. Therefore, particle surface engineering has the potential to decrease the capillary deformation by asymmetric particles via changing their capillary pinning, as well as wetting behavior at fluid interfaces.

Role of Shape in Particle-Lipid Membrane Interactions: From Surfing to Full Engulfment.

Understanding and manipulating the interactions between foreign bodies and cell membranes during endo- and phagocytosis is of paramount importance, not only for the fate of living cells but also for numerous biomedical applications. This study aims to elucidate the role of variables such as anisotropic particle shape, curvature, orientation, membrane tension, and adhesive strength in this essential process using a minimal experimental biomimetic system comprising giant unilamellar vesicles and rod-like particles with different curvatures and aspect ratios. We find that the particle wrapping process is dictated by the balance between the elastic free energy penalty and adhesion free energy gain, leading to two distinct engulfment pathways, tip-first and side-first, emphasizing the significance of the particle orientation in determining the pathway. Moreover, our experimental results are consistent with theoretical predictions in a state diagram, showcasing how to control the wrapping pathway from surfing to partial to complete wrapping by the interplay between membrane tension and adhesive strength. At moderate particle concentrations, we observed the formation of rod clusters, which exhibited cooperative and sequential wrapping. Our study contributes to a comprehensive understanding of the mechanistic intricacies of endocytosis by highlighting how the interplay between the anisotropic particle shape, curvature, orientation, membrane tension, and adhesive strength can influence the engulfment pathway.

Computational modelling of a triaxial vibrating sample magnetometer

Magnetic Field Assisted Additive Manufacturing (MFAAM) enables 3D printing of magnetic materials of various shapes which exhibit a complex anisotropy energy surface containing contributions generated from different origins such as sample, particle, and agglomerate shape anisotropy, flow and field induced anisotropy, and particle crystal anisotropy. These novel magnet shapes require the need to measure the x, y, and z components of the magnetic dipole moment simultaneously to fully understand the magnetic reversal mechanism and unravel the complex magnetic anisotropy energy surface of 3D printed magnetic composites. This work aims to develop a triaxial vibrating sample magnetometer (VSM) by adding a z-coil set to a pre-existing biaxial VSM employing a modified Mallison coil set. The optimum size and location of the sensing coils were determined by modeling the sensitivity matrix of the z-coil set. The designed coil set was implemented using 3D printed spools, a manual coil winder, and gauge 38 copper wire. A 3D printed strontium ferrite nylon composite sample was used to estimate the sensitivity of the z-coils (50 mV/emu). The results herein are applicable for any VSM using a modified Mallison biaxial coil configuration allowing for a quick implementation on pre-existing systems.

Shape anisotropy induced jamming of nanoparticles at liquid interfaces: a tensiometric study.

The intersection of nanotechnology and interfacial science has opened up new avenues for understanding complex phenomena occurring at liquid interfaces. The assembly of nanoparticles at liquid/liquid interfaces provides valuable insights into their interactions with fluid interfaces, essential for various applications, including drug delivery. In this study, we focus on the shape and concentration effects of nanoscale particles on interfacial affinity. Using pendant drop tensiometry, we monitor the real-time interfacial tension between an oil droplet and an aqueous solution containing nanoparticles. We measure two different types of nanoparticles: spherical gold nanoparticles (AuNPs) and anisotropic gold nanorods (AuNRs), each functionalized with surfactants to facilitate interaction at the interface. We observe that the interface equilibrium behaviour is mediated by kinetic processes, namely, diffusion, adsorption and rearrangement of particles. For anisotropic AuNRs, we observe shape-induced jamming of particles at the interface, as evidenced by their slower diffusivity and invariant rearrangement rate. In contrast, the adsorption of spherical AuNPs is dynamic and requires more time to reach equilibrium, indicating weaker interface affinity. By detailed analysis of the interfacial tension data and interaction energy calculations, we show that the anisotropic particle shape achieves stable equilibrium inter-particle separation compared to the isotropic particles. Our findings demonstrate that anisotropic particles are a better design choice for drug delivery applications as they provide better affinity for fluid interface attachment, a crucial requirement for efficient drug transport across cell membranes. Additionally, anisotropic shapes can stabilize interfaces at low particle concentrations compared to isotropic particles, thus minimizing side effects associated with biocompatibility and toxicity.

Dilute suspensions of Janus rods: the role of bond and shape anisotropy.

Nanometer-sized clusters are often targeted due to their potential applications as nanoreactors or storage/delivery devices. One route to assemble and stabilize finite structures consists of imparting directional bonding patterns between the nanoparticles. When only a portion of the particle surface is able to form an inter-particle bond, finite-size aggregates such as micelles and vesicles may form. Building on this approach, we combine particle shape anisotropy with the directionality of the bonding patterns and investigate the combined effect of particle elongation and surface patchiness on the low density assembly scenario. To this aim, we study the assembly of tip-functionalised Janus hard spherocylinders by means of Monte Carlo simulations. By exploring the effects of changing the interaction strength and range at different packing fractions, we highlight the role played by shape and bond anisotropy on the emerging aggregates (micelles, vesicles, elongated micelles, and lamellae). We observe that shape anisotropy plays a crucial role in suppressing phases that are typical to spherical Janus nanoparticles and that a careful tuning of the interaction parameters allows promoting the formation of spherical micelles. These finite-size spherical clusters composed of elongated particles might offer more interstitials and larger surface areas than those offered by micelles of spherical or almost-spherical units, thus enhancing their storage and catalytic properties.

Nanosheet Particles with Defect-Free Block Copolymer Structures Driven by Emulsions Containing Crystallizable Surfactants.

Highly anisotropic-shaped particles with well-ordered internal nanostructures have received significant attention due to their unique shape-dependent photonic, rheological, and electronic properties and packing structures. In this work, nanosheet particles with cylindrical block copolymer (BCP) arrays are achieved by utilizing collapsed emulsions as a scaffold for BCP self-assembly. Highly elongated structures with large surface areas are formed by employing crystallizable surfactants that significantly reduce the interfacial tension of BCP emulsions. Subsequently, the stabilized elongated emulsion structures lead to the formation of BCP nanosheets. Specifically, when polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and 1-octadecanol (C18-OH) are co-assembled within an emulsion, C18-OH penetrates the surfactant layer at the emulsion interface, lowering the interfacial tension (i.e., below 1 mN m-1 ) and causing emulsion deformation. In addition, C18-OH crystallization allows for kinetic arrest of the collapsed emulsion shape during solvent evaporation. Consequently, PS-b-PDMS BCPs self-assemble into defect-free structures within nanosheet particles, exhibiting an exceptionally high aspect ratio of over 50. The particle formation mechanism is further investigated by controlling the alkyl chain length of the fatty alcohol. Finally, the coating behavior of nanosheet particles is investigated, revealing that the deposition pattern on a substrate is strongly influenced by the particle's shape anisotropy, thus highlighting their potential for advanced coating applications.

Effects of particle shape and surface roughness on van der Waals interactions and coupling to dynamics in nanocrystals

The van der Waals interaction between colloids and nanoparticles is one of the key components to understanding particle aggregation, attachment, and assembly. While the ubiquity of anisotropic particle shapes and surface roughness is well-recognized in nanocrystalline materials, the effects of both on van der Waals forces and torques have not been adequately investigated. In this study, we develop a numerical scheme to determine the van der Waals forces and torques between cubic particles with multiple configurations and relative orientations. Our results show that the van der Waals torque due to anisotropic particle shapes is appreciable at nearly all configurations and mutual angles, outcompeting Brownian torque for various materials systems and conditions. Surface roughness enhances this particle shape effect, resulting in stronger van der Waals interactions ascribed to protrusions on the surfaces. Moreover, a scaling analysis indicates that the surface roughness alters the separation dependence of the van der Waals force and, more importantly, significantly influences the dynamics of two approaching particles. Our results clearly demonstrate that surface roughness and anisotropic shape play a crucial role in the energetics and kinetics of various particle-scale and emergent phenomena, such as crystal growth by oriented attachment, nanomaterials synthesis and assembly, mud flow rheology, as well as the deposition of natural nanocrystals within the subsurface.

Unified scaling law for wall friction in laterally confined flows of shape anisotropic particles

Unified scaling law for wall friction in laterally confined flows of shape anisotropic particles

Ultrasound Manipulation and Extrusion of Active Nanorods.

Synthetic self-propelled nano and microparticles have a growing appeal for targeted drug delivery, collective functionality, and manipulation at the nanoscale. However, it is challenging to control their positions and orientations under confinement, e.g., in microchannels, nozzles, and microcapillaries. This study reports on the synergistic effect of acoustic and flow-induced focusing in microfluidic nozzles. In a microchannel with a nozzle, the balance between the acoustophoretic forces and the fluid drag due to streaming flows generated by the acoustic field controls the microparticle's dynamics. This study manipulates the positions and orientations of dispersed particles and dense clusters inside the channel at a fixed frequency by tuning the acoustic intensity. The main findings are: first, this study successfully manipulates the positions and orientations of individual particles and dense clusters inside the channel at a fixed frequency by tuning the acoustic intensity. Second, when an external flow is applied, the acoustic field separates and selectively extrudes shape-anisotropic passive particles and self-propelled active nanorods. Finally, the observed phenomena are explained by multiphysics finite-element modeling. The results shed light on the control and extrusion of active particles in confined geometries and enable applications for acoustic cargo (e.g., drug) delivery, particle injection, and additive manufacturing via printed self-propelled active particles.

Margination of 2D Platelet Microparticles in Blood.

Margination describes the movement of particles toward the endothelial wall within blood vessels. While there have been several studies tracking the margination of spherical particles in blood, the behavior of anisotropic particle shapes is not well described. In this study 2D platelet particles which possess many attractive qualities for use as a drug delivery system, with their high surface area allowing for increased surface binding activity, were directly monitored and margination quantified. The margination propensity of 1 and 2 μm 2D platelet particles was contrasted to that of 2 μm spherical particles at apparent wall shear rates (WSRs) of 50, 100, and 200 s-1 by both directly tracking labeled particles using fluorescent microscopy as well as using small-angle X-ray scattering (SAXS). For fluorescence studies, margination was quantified using the margination parameter M, which describes the number of particles found closest to the walls of a microfluidic device, with an M-value of 0.2 indicating no margination. Increased margination was seen in 2D platelet particles when compared to spherical particles tested at all flow rates, with M-values of 0.39 and 0.31 seen for 1 and 2 μm 2D platelet particles, respectively, while 2 μm spherical particles had an M-value of 0.21. Similarly, margination was observed qualitatively using SAXS, with increased scattering seen for platelet particles near the microfluidic channel wall. For all particles, increased margination was seen at increasing shear rates.

Lyotropic Nematic Phases of Isotropic Nanoparticles via Semiflexible Polymer Ligands.

Lyotropic liquid crystalline(LC) nanomaterials are normally achieved through particle shape anisotropy. Herein, it is shown that lyotropic nematic rather than cubic phases are produced from sphericalnanoparticles (NPs) with semi-flexible polymer ligands. ZrO2 nanocrystals (4nm dia.) are coated with a dense shell of poly(hexyl isocyanate) (PHIC), a helical rod-like polymer that forms lyotropic LC phases in a range of organic solvents. Solvent casted NPs with PHIC ligands above the persistence length form linear assemblies, separated by a characteristic distance related to the chain length while NPs with shorter, rigid rod PHIC ligands pack hexagonally. Concentrated NP-PHIC dispersions present nematic textures similar to the free PHIC nematic solutions but at lower critical concentrations, widening the isotropic-nematic biphasic region. 2 H NMR spectra of the NPs dispersed in a deuterated solvent display quadrupolar splittings that increase with NP concentration, showing that the PHIC ligands are magnetically aligned. The high degree of orientation order is evidence that splaying of the ligand shell transforms the spherical NPs to rod-like shapes that assemble to produce nematic lyotropic LC phases and linear NP arrays. This approach to creating anisotropic assemblies can be extended to other types of spherical NPs and semiflexible polymers.

Mechanochemical Synthesis of Shape-Anisotropic Particles through Wet Milling Using High-Energy Mills

A high-energy ball mill, such as a planetary ball mill, is widely used for preparing a homogeneously mixed powder and reducing particle size. Because of the high impact energy generated by the collision of ball media, the planetary ball milling is expected to produce local high-temperature and high-pressure zones. In wet milling, the solubility of the material varies owing to the local and instantaneous changes caused by the collision. Consequently, mechanochemical reactions through a dissolution–precipitation mechanism can be attained without external heating. In this paper, we show the wet mechanochemical process in water to synthesize functional hydrous or hydrate materials with various shapes, including nanosheets, nanotubes, plates, flakes, rods, and nanoparticles. Morphology-controlled particles can be obtained by only adjusting the milling conditions, such as milling time, ball size, and centrifugal acceleration. Further, the products can be converted into electrode materials for Li-ion batteries, retaining the precursor morphologies. This wet mechanochemical synthesis can be also applied in a bead mill, where mass production and continuous processing are possible. The wet mechanochemical process is a new particle synthesis method that can achieve both grinding and crystal growth.

Combined Influence of Particle Shape and Fabric on the Shear Behaviour of Granular Materials

The anisotropy feature is an important characteristic of granular materials in natural life and is caused by two facts: the anisotropy feature of particle shape, such as an elongated or flattened shape, and the anisotropy feature of the packing fabric, such as the preferable orientation of particle alignment. The discrete element method has been commonly used in the study of meso-mechanics of granular materials and is in our study to simulate the direct shear test with particles of various aspect ratios under different initial orientation alignment conditions for assessing the coupled influence of anisotropy from particle shape and fabric of particle packings on the shear behaviour of granular materials. Analysis results show that anisotropy from the particle shape has the most significant influence on the shear behaviour of a granular packing when the packing has the initial anisotropy fabric of an orientational alignment perpendicular to the shear direction. Moreover, the initial fabric anisotropy of a granular packing has an increasing influence with the rise in anisotropy of particle shape. A combined anisotropic factor is finally introduced to reflect the coupled influence of the shape anisotropy of particles and the fabric anisotropy of particle packings.

Control of Crystallization of PBT-PC Blends by Anisotropic SiO2 and GeO2 Glass Flakes.

Polymer composites and blend systems are of increasing importance, due to the combination of unique and different material properties. Blending polybutylene terephthalate (PBT) with polycarbonate (PC) has been the focus of attention for some time in order to combine thermo-chemical with mechanical resistance. The right compounding of the two polymers is a particular challenge, since phase boundaries between PBT and PC lead to coalescence during melting, and thus to unwanted segregation within the composite material. Amorphization of the semi-crystalline PBT would significantly improve the blending of the two polymers, which is why specific miscibility aids are needed for this purpose. Recent research has focused on the functionalization of polymers with shape-anisotropic glass particles. The advantage of those results from their two-dimensional shape, which not only improves the mechanical properties but are also suspected to act as miscibility aids, as they could catalyze transesterification or act as crystallization modifier. This work presents a process route for the production of PBT-PC blends via co-comminution and an in-situ additivation of the polymer blend particles with anisotropic glass flakes to adjust the crystallinity and therefore enhance the miscibility of the polymers.

Guiding the self-assembly of colloidal diamond.

The assembly of colloidal cubic diamond is a challenging process since the shape and interaction parameters and the thermodynamic conditions where this structure is stable are elusive. The simultaneous use of shape-anisotropic particles and strong directional interactions has proven to be a successful path to exclusively nucleate this structure. Here, using molecular dynamics simulations, we explore in detail the conditions where the nucleation of cubic diamond from tetrahedral building blocks is favored. In particular, we focus on the effect of depletion and DNA-mediated interactions to form and stabilize this cubic diamond crystal. We find that a particular balance between the strength and the range of the depletion interactions enhances the self-assembly of stable cubic diamond, leading to a narrow region where this structure is nucleated. Moreover, we determine that stronger short-range depletion attractions may arrest the system, leading to the formation of percolating diamond networks or fully disordered gel structures. Accordingly, the internal arrangements of these structures exhibit a distinct variation in terms of fractal dimension and the presence of six-membered rings that increasingly acquire internal strain as the arrest gets more pronounced. With these results, we provide a clear route for the self-assembly of cubic colloidal diamond, toward the realization of crystals with superior photonic properties.

2D phase behaviors of colloidal ellipsoids and rods

In recent years, the shape of particles has emerged as a key factor influencing their self-assembly and phase behaviors. Understanding the phase behaviors of systems containing shape anisotropic particles remains challenging. In this mini-review, we will summarize our recent experimental studies on the phase behaviors of colloidal systems in which all or part of particles have anisotropic shapes. We focus on two types of shape anisotropic particles, ellipsoids and rods. In particular, it was found that 1) in equilibrium, the anisotropic particles form a nematic phase in 2D, 2) when quenched, they can form a stable glassy state with a two-step glass transition, and 3) when they are dispersed as impurities in a 2D colloidal crystal of spheres, they can destroy the 2D crystal phase. We will discuss the current challenges in the field.

Exploiting anisotropic particle shape to electrostatically assemble colloidal molecules with high yield and purity

HypothesisColloidal molecules with anisotropic shapes and interactions are powerful model systems for deciphering the behavior of real molecules and building units for creating materials with designed properties. While many strategies for their assembly have been developed, they typically yield a broad distribution or are limited to a specific type. We hypothesize that the shape and relative sizes of colloidal particles can be exploited to efficiently direct their assembly into colloidal molecules of desired valence. ExperimentsWe exploit electrostatic self-assembly of negatively charged spheres made from either polystyrene or silica onto positively charged hematite cubes. We thoroughly analyze the role of the shape and size ratio of particles on the cluster size and yield of colloidal molecules. FindingsUsing a combination of experiments and simulations, we demonstrate that cubic particle shape is crucial to generate high yields of distinct colloidal molecules over a wide variety of size ratios. We find that electrostatic repulsion between the satellite spheres is important to leverage the templating effect of the cubes, leading the spheres to preferentially assemble on the facets rather than the edges and corners of the cube. The sixfold symmetry of cubes favors the assembly of molecules with six, four, and two satellite spheres at appropriate size ratios and interaction strength.Furthermore, we reveal that our protocol is not affected by the specific choice of the material of the colloidal particles. Finally, we show that the permanent magnetic dipole moment of the hematite cubes can be utilized to separate colloidal molecules from non-assembled satellite particles. Our simple and effective strategy might be extended to other templating particle shapes, thereby greatly expanding the library of colloidal molecules that can be achieved with high yield and purity.