Influence of particle shape on mixing rate in rotating drums based on super-quadric DEM simulations

Fundamental research on the flow and mixing of non-spherical particles is critical for industrial production and design. In this paper, the Discrete Element Method (DEM) is used to study the flow and mixing of granular materials in the horizontal rotating drum, and the periodic boundary condition is employed to eliminate end wall effect. Super-quadric elements are adopted to describe spherical and non-spherical particles. The influences of rotating speed, blockiness, and aspect ratio on the mixing rate are investigated by the Lacey mixing index. The results show that the rotating speed has a primary effect on the mixing rate, whereas the effect of the particle shape on the mixing rate is a secondary factor for non-spherical granular systems. Moreover, the mixing rate of spherical and non-spherical particle systems is significantly different. The mixing rate of spheres is the lowest, and the cubes have a higher mixing rate than the cylinders. As the blockiness decreases or aspect ratio deviates from 1.0, the mixing rate decreases. Ordered face-to-face contacts and dense packing structures result in a higher mixing rate. The analysis of kinetic energy shows that particle shape affects the transfer efficiency of external energy to the granular systems. The translational kinetic energy of non-spherical particles is higher than that of spherical particles, and their rotational kinetic energy is lower than that of spheres. Meanwhile, the blockiness enhances the transfer efficiency of external energy to the non-spherical systems; in contrast, the aspect ratio reduces the energy conversion efficiency.     

Synthesis of iron-copper alloy using electrical discharge machining

The present work investigates the novel route for the synthesis of Fe-Cu alloy using electric discharge machining (EDM). The Synthesis of Fe-Cu alloy is difficult by equilibrium processes because of their immiscible nature. An attempt was made to investigate the synthesis of Fe-Cu alloy by EDM process where the discharge can lead to a very high temperature and subsequent quenching to result in alloy formation. The electrode was made up of copper and die steel was used as workpiece. The characterization of generated debris was carried out by X-ray diffraction analysis, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The nano-phase granular particles of Fe-Cu alloy were confirmed by TEM and selected area diffraction pattern analysis. SEM morphology results reveal that the generated particles were both, spherical and non-spherical shape and size ranging between 50?nm and 30?µm. The EDS analysis indicates that the spherical particles were Fe-rich and non-spherical particles were Cu-rich.     

Composites of polypropylene melt blended with synthesized silica nanoparticles

Spherical and layered silica nanoparticles synthesized by the sol-gel method were melt blended with a polypropylene matrix in order to quantify their effect on thermal and mechanical behaviours of the resulting polymer composites. Transmission electron microscopy images showed that spherical nanoparticles were dispersed in the polymer matrix whereas layered particles display tactoid and agglomerated structures. By thermogravimetric analysis, it was observed that independent of the particle aspect ratio, the nanofillers render larger thermal degradation stabilization to the polymer matrix under oxidative conditions than under inert atmosphere. Noteworthy, the largest improvements were found by using spherical nanoparticles in presence of a compatibilizer. These results allow the conclusion that the physical/chemical adsorption of the volatile products on the particle surface during the oxidative degradation is the plausible mechanism behind the thermal stabilization. Tensile stress-strain tests otherwise showed that composites with spherical nanoparticles can display similar or even larger elastic modulus than composites with layered particles showing that the polymer/particle entanglement could be the mechanism for the load transfer in these nanocomposites.     

A New Approach to Assess Gold Nanoparticle Uptake by Mammalian Cells: Combining Optical Dark‐Field and Transmission Electron Microscopy

Toxicological effects of nanoparticles are associated with their internalization into cells. Hence, there is a strong need for techniques revealing the interaction between particles and cells as well as quantifying the uptake at the same time. For that reason, herein optical dark‐field microscopy is used in conjunction with transmission electron microscopy to investigate the uptake of gold nanoparticles into epithelial cells with respect to shape, stabilizing agent, and surface charge. The number of internalized particles is strongly dependent on the stabilizing agent, but not on the particle shape. A test of metabolic activity shows no direct correlation with the number of internalized particles. Therefore, particle properties besides coating and shape are suspected to contribute to the observed toxicity.     

Modeling particle shape-dependent dynamics in nanomedicine

One of the major challenges in nanomedicine is to improve nanoparticle cell selectivity and adhesion efficiency through designing functionalized nanoparticles of controlled sizes, shapes, and material compositions. Recent data on cylindrically shaped filomicelles are beginning to show that non-spherical particles remarkably improved the biological properties over spherical counterpart. Despite these exciting advances, non-spherical particles have not been widely used in nanomedicine applications due to the lack of fundamental understanding of shape effect on targeting efficiency. This paper intends to investigate the shape-dependent adhesion kinetics of non-spherical nanoparticles through computational modeling. The ligand-receptor binding kinetics is coupled with Brownian dynamics to study the dynamic delivery process of nanorods under various vascular flow conditions. The influences of nanoparticle shape, ligand density, and shear rate on adhesion probability are studied. Nanorods are observed to contact and adhere to the wall much easier than their spherical counterparts under the same configuration due to their tumbling motion. The binding probability of a nanorod under a shear rate of 8 s(-1) is found to be three times higher than that of a nanosphere with the same volume. The particle binding probability decreases with increased flow shear rate and channel height. The Brownian motion is found to largely enhance nanoparticle binding. Results from this study contribute to the fundamental understanding and knowledge on how particle shape affects the transport and targeting efficiency of nanocarriers, which will provide mechanistic insights on the design of shape-specific nanomedicine for targeted drug delivery applications.     

Mechanism for the Cellular Uptake of Targeted Gold Nanorods of Defined Aspect Ratios

Biomedical applications of non‐spherical nanoparticles such as photothermal therapy and molecular imaging require their efficient intracellular delivery, yet reported details on their interactions with the cell remain inconsistent. Here, the effects of nanoparticle geometry and receptor targeting on the cellular uptake and intracellular trafficking are systematically explored by using C166 (mouse endothelial) cells and gold nanoparticles of four different aspect ratios (ARs) from 1 to 7. When coated with poly(ethylene glycol) strands, the cellular uptake of untargeted nanoparticles monotonically decreases with AR. Next, gold nanoparticles are functionalized with DNA oligonucleotides to target Class A scavenger receptors expressed by C166 cells. Intriguingly, cellular uptake is maximized at a particular AR: shorter nanorods (AR = 2) enter C166 cells more than nanospheres (AR = 1) and longer nanorods (AR = 4 or 7). Strikingly, long targeted nanorods align to the cell membrane in a near‐parallel manner followed by rotating by ≈90° to enter the cell via a caveolae‐mediated pathway. Upon cellular entry, targeted nanorods of all ARs predominantly traffic to the late endosome without progressing to the lysosome. The studies yield important materials design rules for drug delivery carriers based on targeted, anisotropic nanoparticles.     

Nanotoxicology: Advanced Optical Imaging Reveals the Dependence of Particle Geometry on Interactions Between CdSe Quantum Dots and Immune Cells (Small 3/2011)

The biocompatibility and possible toxicological consequences of engineered nanomaterials, including quantum dots (QDs) due to their unique suitability for biomedical applications, remain intense areas of interest. We utilized advanced imaging approaches to characterize the interactions of CdSe QDs of various sizes and shapes with live immune cells. Particle diffusion and partitioning within the plasma membrane, cellular uptake kinetics, and sorting of particles into lysosomes were all independantly characterized. Using high‐speed total internal reflectance fluorescence (TIRF) microscopy, we show that QDs with an average aspect ratio of 2.0 (i.e., rod‐shaped) diffuse nearly an order of magnitude slower in the plasma membrane than more spherical particles with aspect ratios of 1.2 and 1.6, respectively. Moreover, more rod‐shaped QDs were shown to be internalized into the cell 2‐3 fold more slowly. Hyperspectral confocal fluorescence microscopy demonstrates that QDs tend to partition within the cell membrane into regions containing a single particle type. Furthermore, data examining QD sorting mechanisms indicate that endocytosis and lysosomal sorting increases with particle size. Together, these observations suggest that both size and aspect ratio of a nanoparticle are important characteristics that significantly impact interactions with the plasma membrane, uptake into the cell, and localization within intracellular vesicles. Thus, rather than simply characterizing nanoparticle uptake into cells, we show that utilization of advanced imaging approaches permits a more nuanced and complete examination of the multiple aspects of cell‐nanoparticle interactions that can ultimately aid understanding possible mechanisms of toxicity, resulting in safer nanomaterial designs.     

Advanced optical imaging reveals the dependence of particle geometry on interactions between CdSe quantum dots and immune cells

The biocompatibility and possible toxicological consequences of engineered nanomaterials, including quantum dots (QDs) due to their unique suitability for biomedical applications, remain intense areas of interest. We utilized advanced imaging approaches to characterize the interactions of CdSe QDs of various sizes and shapes with live immune cells. Particle diffusion and partitioning within the plasma membrane, cellular uptake kinetics, and sorting of particles into lysosomes were all independantly characterized. Using high-speed total internal reflectance fluorescence (TIRF) microscopy, we show that QDs with an average aspect ratio of 2.0 (i.e., rod-shaped) diffuse nearly an order of magnitude slower in the plasma membrane than more spherical particles with aspect ratios of 1.2 and 1.6, respectively. Moreover, more rod-shaped QDs were shown to be internalized into the cell 2-3 fold more slowly. Hyperspectral confocal fluorescence microscopy demonstrates that QDs tend to partition within the cell membrane into regions containing a single particle type. Furthermore, data examining QD sorting mechanisms indicate that endocytosis and lysosomal sorting increases with particle size. Together, these observations suggest that both size and aspect ratio of a nanoparticle are important characteristics that significantly impact interactions with the plasma membrane, uptake into the cell, and localization within intracellular vesicles. Thus, rather than simply characterizing nanoparticle uptake into cells, we show that utilization of advanced imaging approaches permits a more nuanced and complete examination of the multiple aspects of cell-nanoparticle interactions that can ultimately aid understanding possible mechanisms of toxicity, resulting in safer nanomaterial designs.     

Synthesis of biomolecule-modified mesoporous silica nanoparticles for targeted hydrophobic drug delivery to cancer cells

Synthetic methodologies integrating hydrophobic drug delivery and biomolecular targeting with mesoporous silica nanoparticles are described. Transferrin and cyclic-RGD peptides are covalently attached to the nanoparticles utilizing different techniques and provide selectivity between primary and metastatic cancer cells. The increase in cellular uptake of the targeted particles is examined using fluorescence microscopy and flow cytometry. Transferrin-modified silica nanoparticles display enhancement in particle uptake by Panc-1 cancer cells over that of normal HFF cells. The endocytotic pathway for these particles is further investigated through plasmid transfection of the transferrin receptor into the normal HFF cell line, which results in an increase in particle endocytosis as compared to unmodified HFF cells. By designing and attaching a synthetic cyclic-RGD, selectivity between primary cancer cells (BT-549) and metastatic cancer cells (MDA-MB 435) is achieved with enhanced particle uptake by the metastatic cancer cell line. Incorporation of the hydrophobic drug Camptothecin into these two types of biomolecular-targeted nanoparticles causes an increase in mortality of the targeted cancer cells compared to that caused by both the free drug and nontargeted particles. These results demonstrate successful biomolecular-targeted hydrophobic drug delivery carriers that selectively target specific cancer cells and result in enhanced drug delivery and cell mortality.     

An atomic force microscope study of carbon onions and related nanoparticles

Carbon onions are found along with carbon nanotubes and other carbon nanoparticles in the cathodic deposit in the arc-vaporization of graphite. Atomic force microscopy has been used to characterize these particles on the basis of their sizes and shapes. Onion-like particles have three-dimensional, near spherical structure and are distinct from two-dimensional graphitic particles. The spherical shape and height to diameter ratios obtained using atomic force microscope, afford a distinction between onion-like structures and other carbon nanoparticles.     

A combined physical and DEM modelling approach to investigate particle shape effects on load movement in tumbling mills

The discrete element method (DEM) which is used to simulate granular flows often assumes spherical shape for particles. This assumption is legitimized by the added complexity of non-spherical shape representation, contact detection and computational cost. In this work, the difference between the dynamics of non-spherical and spherical particles was studied in detail by a combined physical and DEM modeling approach. An in-house developed DEM software called KMPC_DEM©, which was coded to handle non-spherical particles, was used to simulate the behavior of particles. To calibrate the model parameters, a model tumbling mill (100 cm diameter and 10.8 cm length) with one transparent end was used which made accurate photography possible. The tests were performed at filling of 20% and mill speed of 85% of critical speed with steel balls and wood cubes. In the simulation, each cubical particle was represented with clusters of spheres (with identical size) by particle packing algorithm for contact detection and contact-force calculation. Comparison of the simulation and experimental results showed that the difference between the measured and predicted impact toe, shoulder angle and bulk toe angle were 3, 4 and 5°, respectively. The significant change in the charge movement and structure on account of non-spherical particles was reflected in the amount of in-flight charge, and positions of shoulder, impact toe and bulk toe. It found that there was a 17% difference in the amount of in-flight of charge between cubical and spherical particles. The marked difference was attributed to higher interlocking of non-spherical particles in comparison to spherical balls. The results showed that cubical particles participated 5% more in the high energy impact action compared to that of the spherical particles. The simulation computation time increased by 35 times when the shape of particles changed from spherical to cubical.     

Shape-memory nanoparticles from inherently non-spherical polymer colloids

Samples of polymeric materials generally have no intrinsic shape; rather their macroscopic form is determined by external forces such as surface tension and memory of shear (for example, during extrusion, moulding or embossing). Hence, in the molten state, the thermodynamically most stable form for polymer (nano)particles is spherical. Here, we present the first example of polymer nanoparticles that have an intrinsic non-spherical shape. We observe the formation of high-aspect-ratio ellipsoidal polymer nanoparticles, of controlled diameter, made from main-chain liquid crystalline polymers using a mini-emulsion technique. The ellipsoidal shape is shown to be an equilibrium (reversible) characteristic and a direct result of the material shape memory when a liquid crystal nanoparticle is in its monodomain form.     

DEM investigations of failure mode of sands under oedometric loading

It will be practically useful to explore the evolutions of the failure modes of sand grains within a sand specimen subject to compression for the particle breakage research. This paper attempts to deal with this challenge by conducting a discrete element method (DEM) simulation study on oedometric compression of two kinds of sands (spherical and non-spherical particles). In this study, particle morphologies reconstructed by the spherical harmonic (SH) analysis were created using the agglomerate method, and the micro-parameters used to define the contact model and the properties of walls and balls were adopted based on the single particle crushing tests. The effects of particle shape on the crushing behavior of granular materials and on the evolutions of failure modes of sand grains were captured, and the experimental data was used to evaluate the feasibility and reliability of the proposed DEM modelling strategy. The simulation results show that particle shape affects not only the number, type and orientation of cracks but also the evolution of the particle failure modes. The failure mode of chipping is the most common way to crush for both spherical and non-spherical particles. The particles that have less aspect ratio, sphericity and convexity are more likely to experience the failure mode of comminution. These findings shed light on the key role of particle shape in the investigation of the failure mode of sand grains and facilitate a better understanding of grain-scale behavior of granular materials.     

Synthesis of au nanoparticles at "all" pH by H2O2 reduction of HAuCl4

In this article we report the synthesis of Au nanoparticles (NPs), from HAuCl4, in the pH range of 2.9 to 11.2 using H2O2 as the reducing agent. Ultraviolet-visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction techniques have been used to characterize the Au NPs. UV-Vis spectral observation showed that the Au NPs synthesized in acidic conditions tend to generate particles with absorption maximum around 540 nm. On the other hand the NPs generated at a pH higher than 8.0 generally have broad absorption with maxima occurring beyond 600 nm. Interestingly, TEM analysis showed that the NPs generated at pH lower than 7.0 tend to be smaller and spherical in shape, whereas the particles generated at a pH beyond 7.0 tend to be non-spherical and larger in sizes or agglomeration of small particles. Also, we speculate on the mechanisms of reduction of HAuCl4 by H2O2 under different pH conditions.     

一种非球形纳米二氧化硅颗粒制备新方法

以低成本工业级硅酸钠为原料,采用离子交换法制备了非球形纳米二氧化硅颗粒。在制备过程中,采用控制无机碱催化剂1%(质量分数)氢氧化钠水溶液滴加到活性硅酸速度的方法来控制二氧化硅晶核成核的形貌,进而控制二氧化硅颗粒的形貌,避免了传统方法(通过引入有机碱或者引入二价或三价阳离子)制备非球形二氧化硅颗粒的不足。扫描电镜显示所制备的二氧化硅颗粒为非球形(呈花生、哑铃或枣状),轴向粒径为10~20nm,径向粒径为45~80nm。激光粒度分析仪测试表明非球形颗粒高斯分布平均粒径为39.0nm,多分散指数高达0.261。该方法制备非球形二氧化硅颗粒步骤简单、环境友好,非常有利于工业化生产与应用。     

Thirty-femtogram detection of iron in mammalian cells

Inorganic nanomaterials and particles with enhanced optical, mechanical, or magnetic attributes are currently being developed for a wide range of applications. Safety issues have developed however concerning their potential cyto- and genotoxicity. For in vivo and in vitro experimentations, recent developments have heightened the need for simple and facile methods to measure the amount of nanoparticles taken up by cells or tissues. In this work, a rapid and highly sensitive method for quantifying the uptake of iron oxide nanoparticles in mammalian cells is reported. The approach exploits the digestion of incubated cells with concentrated hydrochloric acid reactant and a colorimetric-based UV-visible absorption technique. The technique allows the detection of iron in cells over 4 decades in masses from 0.03 to 300 picograms per cell. Applied on particles of different surface chemistry and sizes, the protocol demonstrates that the coating is the key parameter in the nanoparticle/cell interactions. The data are corroborated by scanning and transmission electron microscopy, and the results stress the importance of resiliently adsorbed nanoparticles at the plasma membrane.     

Numerical study on deposition of non-spherical shaped particles in cascade impactor

This study investigated the deposition of non-spherical particles in a cascade impactor using numerical simulations based on computational fluid dynamics and a discrete phase model (CFD-DPM). An optimum drag force model of non-spherical particles was used to calculate the dynamic behavior of the needle-shaped particles. The trajectory of these particles in an elbow pipe was computed and measured using a high-speed video camera. The computed trajectory agreed well with the experimental trajectory, and it was confirmed that the drag force model of non-spherical particles correctly expressed the drag force in the CFD-DPM numerical simulation. Next, the motion of the needle-shaped particles in a cascade impactor was numerically simulated and compared with that in the experimental results. The simulated classification efficiency agreed well with the experimental results. Additionally, the relationship between the aspect ratio of the needle-shaped particles and their behavior in the cascade impactor was numerically analyzed. The cut-off diameter decreased with the aspect ratio at a 50% classification efficiency in the cascade impactor. This was because the drag force of the particle was assumed to increase with the aspect ratio, and longer particles fell at a lower stage in the cascade impactor.     

Quantitative assessment of the comparative nanoparticle-uptake efficiency of a range of cell lines

The mechanism(s) of nanoparticle-cell interactions are still not understood. At present there is little knowledge of the relevant length- and timescales for nanoparticle intracellular entry and localization within cells, or the cell-specificity of nanoparticle uptake and localisation. Here, the effect of particle size on the in-vitro intracellular uptake of model fluorescent carboxyl-modified polystyrene nanoparticles is investigated in various cell lines. A range of micro- and nanoparticles of defined sizes (40 nm to 2 μm) are incubated with a series of cell types, including HeLa and A549 epithelial cells, 1321N1 astrocytes, HCMEC D3 endothelial cells, and murine RAW 264.7 macrophages. Techniques such as confocal microscopy and flow cytometry are used to study particle uptake and subcellular localisation, making significant efforts to ensure reproducibility in a semiquantitative approach. The results indicate that internalization of (nano)particles is highly size-dependent for all cell lines studied, and the kinetics of uptake for the same type of nanoparticle varies in the different cell types. Interestingly, even cells not specialized for phagocytosis are able to internalize the larger nanoparticles. Intracellular uptake of all sizes of particles is observed to be highest in RAW 264.7 cells (a specialized phagocytic cell line) and the lowest in the HeLa cells. These results suggest that (nano)particle uptake might not follow commonly defined size limits for uptake processes, and highlight the variability of uptake kinetics for the same material in different cell types. These conclusions have important implications for the assessment of the safety of nanomaterials and for the potential biomedical applications of nanoparticles.     

Preparation of hollow spherical magnetite nanoparticles

We have developed and tested procedures for the synthesis of hollow spherical magnetite nanoparticles and analyzed the general mechanisms of their formation in relation to their structure and morphology. The phase composition, elemental composition, and morphology of the synthesized particles have been examined by X-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy, and their magnetic properties have been studied by an induction method using a vibrating sample magnetometer. The results demonstrate that the proposed procedures enable the preparation of hollow porous spherical magnetite particles 40 nm to 100 μm in diameter, with a wall thickness ≃d/10 and a narrow size distribution.     

Angle of repose and stress distribution of sandpiles formed with ellipsoidal particles

The properties of a sandpile such as angle of repose and stress distribution are affected by many variables, among which particle shape is one of the most important. In this work, ellipsoids which can represent a large range of shapes varying from disk- to cylinder-type are used. The discrete element method is employed in order to conduct controlled numerical experiments. The results confirm the general findings reported in the literature. It also shows that with aspect ratios deviating from 1.0, the angle of repose increases significantly, but disk-type shape and cylinder-type shape follow different variation trends. Empirical correlations between the angle of repose and aspect ratio or sphericity are proposed. The analysis on the stress distribution shows that particle shape affects the magnitude of the normal contact force between particles significantly, with spheres being the smallest. The pressure distribution underneath sandpiles is featured with a relatively constant normal pressure in the central region rather than a dip. It is confirmed that non-spherical particles have more pronounced stress dip than spherical particles.