A method for assessing nanomaterial dispersion quality based on principal component analysis of particle size distribution data

Seemingly contradictory findings between studies are a major issue in nanoecotoxicological research and have been explained as a result of the lack of comparability between assay methods,with dispersion of nanomaterials being identified as a key factor.Here we show the use of a multivariate method,principal component analysis(PCA),as a tool in protocol development and categorization of dispersion quality.Results show the significance of particle concentration within a protocol,and its effect on repeatability.Our results suggest that future studies should involve the use of PCA as a powerful data exploration tool to facilitate method development,comparability and integration of data across different laboratories.     

A method for assessing nanomaterial dispersion quality based on principal component analysis of particle size distribution data

Seemingly contradictory findings between studies are a major issue in nanoecotoxicological research and have been explained as a result of the lack of comparability between assay methods, with dispersion of nanomaterials being identified as a key factor. Here we show the use of a multivariate method, principal component analysis (PCA), as a tool in protocol development and categorization of dispersion quality. Results show the significance of particle concentration within a protocol, and its effect on repeatability. Our results suggest that future studies should involve the use of PCA as a powerful data exploration tool to facilitate method development, comparability and integration of data across different laboratories.     

稀疏两相湍流的惯性颗粒倾向性弥散

气相采用大涡模拟、颗粒相采用拉格朗日轨道模型的方法对后台阶突扩流、充分发展槽道流和圆湍射流3种典型的稀疏气固两相流动进行了数值模拟,研究了颗粒倾向性弥散的特征和规律. 研究表明颗粒的跟随性和倾向性相联系,颗粒惯性和大涡结构同时决定颗粒的倾向性分布特征. Stokes数量级为1(气相时间参考尺度取为宏观特征时间尺度)左右的颗粒,倾向性分布特征最强烈. 颗粒倾向分布于低涡量(或是低脉动速度)的湍流区域.      

Rotational and translational diffusivities of germanium nanowires

Understanding the rheological behavior of dilute dispersions of cylindrical nanomaterials in fluids is the first step towards the development of rheological models for these materials. Individual particle tracking was used to quantify the rotational and translational diffusivities of high-aspect-ratio germanium nanowires in alcohol solvents at room temperature. In spite of their long lengths and high aspect ratios, the rods were found to undergo Brownian motion. This work represents the first time that the effects of solvent viscosity and confinement have been directly measured and the results compared to proposed theoretical models. Using viscosity as a single adjustable parameter in the Kirkwood model for Brownian rods was found to be a facile and versatile way of predicting the diffusivities of nanowires across a broad range of length scales.     

Toxicity of manufactured nanomaterials

Manufactured nanomaterials with unique properties have been extensively applied in various industrial, agricultural or medical fields. However, some of the properties have been identified to be closely related to nanomaterial toxicity. The “nano-paradox” has aroused concerns over the use and development of nanotechnology, which makes it difficult for regulatory agencies to regulate nanomaterials. The key to fulfilling proper nanomaterial regulation lies in the adequate understanding of the impact of nanomaterial properties on nano-bio interactions. To this end, we start the present work with a brief introduction to nano-bio interactions at different levels. Based on that, how key toxicity-associated properties of manufactured nanomaterials (i.e., size, shape, chemical composition, surface properties, biocorona formation, agglomeration and/or aggregation state, and biodegradability) impact their toxicokinetics, cellular uptake, trafficking and responses, and toxicity mechanisms is deeply explored. Moreover, advanced analytical methods for studying nano-bio interactions are introduced. Furthermore, the current regulatory and legislative frameworks for nanomaterial-containing products in different regions and/or countries are presented. Finally, we propose several challenges facing the nanotoxicology field and their possible solutions to shed light on the safety evaluation of nanomaterials.     

Numerical investigation of droplet pre-dispersion in a monodisperse droplet spray dryer

Monodisperse droplet spray dryers have great advantages in particle formation through spray drying because of their ability to produce uniform sized particles. Experimental analyses of this system have shown that droplets atomized through the piezoceramic nozzle need to be sufficiently well dispersed before entering the drying chamber to achieve sufficiently dried particles. However, the dispersion dynamics cannot be readily observed because of experimental limitations, and key factors influencing the dispersion state currently remain unclear. This study carried out numerical simulations for droplet dispersions in the dispersion chamber, which allow this important process to be visualized. The systematic and quantitative analyses on the dispersion states provide valuable data for improving the design of the dispersion chamber, and optimizing the spray drying operation.     

Rheological characterization of bimodal colloidal dispersions

In order to investigate the effect of the particle size distribution on the rheological properties of concentrated colloidal dispersions both steady-state shear and oscillatory measurements have been performed on well-characterized bimodal dispersions of sterically stabilized PMMA particles. Replacing a minor amount of large particles by small ones in a concentrated dispersion, keeping the total effective volume fraction constant, decreases the viscosity quite drastically. On the other hand, replacing a small amount of small particles by big ones hardly effects the viscosity at all. This behavior can be attributed to the deformability of the stabilizing polymer layer. A procedure is proposed to calculate the limiting viscosities in a bimodal colloidal dispersion starting from the characteristics of the monodisperse systems. A good agreement has been obtained between the calculated values and the experimental results. The linear viscoelastic properties of the concentrated dispersions have been investigated by means of oscillatory measurements. The plateau values of the storage modulus for the bimodal dispersions decrease with an increasing fraction of the coarse particles. By substituting the bimodal dispersion by an equivalent monodisperse system the storage modulus can be superimposed on the values for the monodisperse suspensions when plotted as a function of the mean interparticle distance.     

Dispersion Stability and Transport of Nanohybrids through Porous Media

Single-walled carbon nanotube-silica nanohybrid particles are a very promising material that could be used for enhanced oil recovery because of their interfacial activity. To demonstrate the basic principle, aqueous nanohybrid particle dispersions were evaluated by looking at the effect of pH, surfactant, and polymer. The results showed that pH did not have significant effect on the dispersion stability of nanohybrid particles. Although surfactant could improve the dispersion stability, it reduced the interfacial activity of the nanohybrid particles, causing them to stay in the aqueous phase. The best nanohybrid particle dispersion stability was found upon polymer addition, where the dispersions were stable for more than a week even at low polymer concentration (50?ppm). One-dimensional sand-pack studies were performed to evaluate the flow of the nanohybrid particles through porous media. The results showed that most of the nanohybrid particles (>99%) could pass through a column packed with glass beads while a measurable fraction of the particles was retained in the column packed with crushed Berea. When the columns contained a residual saturation of decane, additional nanohybrid particles were retained at the oil/water interface in both glass beads and crushed Berea sand media. The sand pack studies showed that not only can the nanohybrid particles flow through porous media but also about half of the particles injected will go the O/W interface when the porous medium contains a residual saturation of hydrocarbon, where they could be used to support a catalytic conversion of components of the oil in reservoirs.     

Effect of Sample Pre-Contact on the Experimental Evaluation of Cartilage Mechanical Properties

Mechanical characterization of articular cartilage has been widely analyzed in the literature, both experimentally and numerically, since load support (strength) and deformability (compliance) are among the most important physiological functions of this living tissue. They are also important indicators of cartilage degradation and regeneration. Cartilage elastic properties (Young’s Modulus, Aggregate Modulus and Poisson ratio) are usually determined experimentally by uniaxial confined and unconfined compression tests. Relevant differences can be found in the literature for these variables even when similar experimental protocols are used. Before starting the actual compression test, a pre-contact protocol has to be carried out in order to obtain optimum contact between the test tool and the cartilage sample. The aim of this work is to analyze the effect of sample pre-contact on the test results comparing three different protocols available in the literature (predeformation of 4 and 10 % of the total thickness of the sample and a preload equivalent to 12.5 KPa). The implementation of these protocols achieved contact, but only the predeformation allowed normalized experiments and ensured repeatability of the tests. Additionally, under the predeformation protocols, the results and trends for uniaxial compression tests were consistent with the cartilage physiological function. However, for 10 % predeformation, the experimental data showed maximum dispersion at the final stress levels. The statistical treatment determined significant differences between the 10 % predeformation and the preload results (Aggregate Modulus and Poisson ratio), defining them as non comparable protocols. Finally, a new pre-contact protocol is proposed introducing an initial approximation point between the test tool and the cartilage sample, and followed by a predeformation of 4 % for confined and unconfined tests.     

Micron-scale origin of the shear-induced structure in Laponite–poly(ethylene oxide) dispersions

We study the transient response to simple shear of aqueous dispersions of Laponite clay particles and poly(ethylene oxide) at concentrations for which shear induces structure in the form of a network of polymer–clay bonds. We examine the effects of shear on the structure at the micrometer length scale. Bulk rheometric measurements give the material’s response to step changes in shear rate. We find that a critical value of the shear rate separates two regions with different rheological behaviors. Static small-angle light scattering shows a corresponding qualitative change in the anisotropy of the dispersion under shear at the micron scale. We interpret our results in terms of the effects of shear on the interactions between clay particles and polymer chains and on the aggregation mechanisms in the dispersion.     

Determination of particle exchange rates at over-flow weirs in horizontal fluidised beds by particle tracking velocimetry

Residence time distributions (RTDs) in horizontal fluidised beds have a huge effect on solid product properties and are influenced by the internal design of the apparatus, e.g. the separation into different compartments by weirs. Weirs can be passed in or against the overall solid transport direction, with the back-flow resulting in axial dispersion, which is a measure of the spread of the RTD. Therefore, the ratio of exchange rates at weirs under different fluidisation conditions provides information on axial dispersion. In this work, a methodology based on particle tracking velocimetry is presented to obtain information on the exchange rates of particles at weirs in horizontal fluidised beds. The internal recirculation is studied for over-flow weirs with respect to different fluidisation conditions, providing a first step towards determining the effects of weirs and fluidisation conditions on axial dispersion and RTDs in horizontal fluidised beds.     

Particle dispersion in a single-sided backward-facing step flow

The paper describes the particle dispersion in a single-sided backward-facing step flow. Particles of well-known sizes in the diameter range from 1 to 70 μm were suspended in an air flow and the particle motion over a step was measured by mean of a laser-Doppler anemometer. Thus, the local and integral flow quantities, i.e. the mean and turbulent velocity data could be measured precisely. In the experiments, monodispersed particle size distributions were used to exclude particle size related information ambiguity, known as triggering effects or size bias. The results of this study show qualitatively and quantitatively the difference in time-averaged particle dynamics for selected particle sizes in a backward-facing step flow. The experiments show, for different sizes, the changes in the particle velocity field in comparison with the velocity field of the continuous phase deduced from the 1 μm particles, and also imply the strong influences which different particle sizes have on flow data evaluation when size effects are not taken into account with particle-related optical measuring techniques.     

Rheological properties of PDMS/clay nanocomposites and their sensitivity to microstructure

The effect of microstructure on the rheology of clay/polymer nanocomposites is investigated using dispersions of organically treated clay in nearly Newtonian poly(dimethylsiloxane). Degree of dispersion and floc size are altered by using two different dispersion procedures and by changing the shear history. The scaling for dynamic moduli of attractive colloids applies, except for a possible relaxation mechanism at very low frequencies. The time to reach the crossover at a given frequency is found to be extremely sensitive to the dispersion procedure used. Hydrodynamic and elastic components of the steady state stress, on the other hand, evolve in a very similar fashion for the different systems. Although the relaxation times of the elastic stress components change drastically with flow-induced changes in structure, the dispersion process hardly has an effect at all. Intermittent start-up flows in the forward and reverse directions show that anisotropy persists long after the flow has been arrested, even at shear rates where no large reversible flocs are present. The degree of dispersion only had a limited effect on the anisotropy. Finally, the effect of shear on structure recovery has been studied. Very low shear rates are found to increase the rate of recovery, even for small strains.     

Process splitting of the boundary conditions for the advection–dispersion equation

Rational strategies are considered for the specification of the intermediate boundary condition at an inflow boundary where process splitting (fractional steps) is adopted in solving the advection–dispersion equation. Three lowest-order methods are initially considered and evaluation is based on comparisons with an analytical solution. For flow and dispersion parameter ranges typical of rivers and estuaries, the given boundary condition for the complete advection–dispersion equation at the end of the complete time step provides a satisfactory estimate of the intermediate boundary value. This was further confirmed by the development and evaluation of two higher-order methods. These required non-centred discrete approximations for spatial derivatives, which offset any special advantages from the higher truncation error order.     

Effect of drag force on backward-facing step gas-particle turbulent flows

An improved drag force coefficient of gas-particle interaction based on the traditional Wen’s 1966 model is proposed. In this model, a two-stage continuous function is used to correct the discontinuous switch when porosity less than 0.2. Using this proposed correlation and the Wen’s 1966 model, a gas-particle kinetic energy and particle temperature model is developed to predict the hydrodynamic characteristics in backward-facing step gas-particle two-phase turbulent flows. Numerically results showed that they are in good agreement with experiment measurements and presented model are better due to a improvement of momentum transport between gas and particle phases. Particle dispersions take on the distinctively anisotropic behaviors at every directions and gas phase fluctuation velocity are about twice larger than particle phases. Particle phase has a unique transportation mechanism and completely different from the gas phase due to different density. Furthermore, the correlation values of axial–axial gas-particle are always greater than the radial–radial values at fully flow regions. The gas-particle two-phase interactions will make influence on two-phase turbulent flow behaviors.     

Rheological properties of poly(dimethylsiloxane) filled with fumed silica: I. Hysteresis behaviour

The apparent viscosity and primary normal stress difference were measured for dispersions of fumed silica in poly(dimethylsiloxane). Dispersions with less than 4.75% by weight of filler exhibit hysteresis in both the viscosity and normal stress, when the shear rate was increased and then decreased in discrete steps. The shape of the hysteresis loops were sensitive to the details of the deformation history. By using the appropriate deformation history, the material properties determined during the increasing shear rate part of the hysteresis experiment compare favourably with the steady-state rheological properties. The rheological properties of the dispersion were quite sensitive to the age of the fluid with no hysteresis behaviou exhibited by dispersions less than three days old. For dispersions with at least 4.75% by weight of fumed silica, neither the apparent viscosity nor the primary normal stress coefficient exhibited significant hysteresis behaviour. The relationship between the observed rheological behaviour and the dispersion's microstructure is discussed.     

Processing and characterization of biodegradable polymer nanocomposites: detection of dispersion state

Nanobiocomposites of poly(lactic acid) (PLA) with 3–5 wt% organically modified montmorillonite (OMMT) were prepared by melt compounding in two different mixers, miniature twin-screw extruder and internal batch mixer, leading to different degrees of dispersion. The progress of dispersion was characterized by melt rheology coupled with light attenuation. Processed PLA/OMMT samples showed percolating networks in the melt, detected by a step increase in low-frequency elastic moduli. The melt elasticity of nanocomposites increased, while the light attenuation coefficient and the loss tangent decreased progressively with mixing energy and reached saturation that can be attributed to the maximum level of clay dispersion achieved in the present experimental conditions. Results showed that a combination of low-frequency loss tangent and light attenuation coefficient provides a potentially sensitive method for the characterization of the degree of clay dispersion. The direct correlation between light attenuation coefficient and loss tangent follows linear dependence and may open an approach for the rapid inline analysis of the degree of dispersion in melt-processed nanocomposites.     

Establishing foundations of the mechanics of nanocomposites (Review)

A general idea of the mechanics of nanocomposites that allows formulating a system of approaches and methods of analysis in this area is given. The place of mechanics in materials research and the structural levels that divide mechanics into macromechanics, mesomechanics, micromechanics, and nanomechanics are discussed. A brief historical sketch of the nanomaterial technology is presented. Examples of different nanotechnologies and nanomaterials are given. Typical nanomaterials and their properties are described. Matrices and reinforcements of nanocomposite materials as well as their properties are considered separately. A classification of nanocomposites is proposed. Special attention is given to modeling in the structural mechanics of nanocomposites, the principles of continualization and homogenization, edge and near-surface effects, validity limits of the continuum approach, and two-sided estimates. A discussion is given of two basic models within the framework of the basic approach as a set of concepts, models, and problem statements and of the development of methods adequately describing mechanical phenomena in nanocomposites. The presented material is mainly taken from the book A. N. Guz, J. J. Rushchitsky, and I. A. Guz, Introduction to the Mechanics of Nanocomposites [in Russian], S. P. Timoshenko Inst. Mech., Kyiv (2010)     

混合层中粒子扩散的实验研究

本文应用流动显示和LDA测量,对混合层中粒子的扩散问题进行了实验研究。结果表明：粒子的扩散强烈地依赖于St数,具有较小St的粒子的扩散近似地与流体示踪粒子相同,随着St的增大,扩散角度增大,也就是说粒子扩散加快,并且随着粒子惯性的增大,它对湍流脉动的响应将会减弱。     

Analysis of multifluid flows with large time steps using the particle finite element method

Multifluids are those fluids in which their physical properties (viscosity or density) vary internally and abruptly forming internal interfaces that introduce a large nonlinearity in the Navier–Stokes equations. For this reason, standard numerical methods require very small time steps in order to solve accurately the internal interface position. In a previous paper, the authors developed a particle‐based method (named particle finite element method (PFEM)) based on a Lagrangian formulation and FEM for solving the fluid mechanics equations for multifluids. PFEM was capable of achieving accurate results, but the limitation of small time steps was still present. In this work, a new strategy concerning the time integration for the analysis of multifluids is developed allowing time steps one order of magnitude larger than the previous method. The advantage of using a Lagrangian solution with PFEM is shown in several examples. All kind of heterogeneous fluids (with different densities or viscosities), multiphase flows with internal interfaces, breaking waves, and fluid separation may be easily solved with this methodology without the need of small time steps. Copyright © 2014 John Wiley & Sons, Ltd.