Progress in nanoparticles characterization: Sizing and zeta potential measurement

Characterization of various nanoparticles is on the center stage in nanotechnology development. The subjects for nanoparticles characterization are focused on particle size and particle surface charge determinations. This article summarizes the latest development in particle size analysis using dynamic light scattering and surface charge determination using electrophoretic light scattering for nano-or even sub-nanoparticles in concentrated suspensions.     

Effect of nanoparticle concentration on zeta-potential measurement results and reproducibility

The effect of nanoparticle concentration on zeta-potential measurement results at dilute concentrations was evaluated.The values of the zeta-potential for four different types of nanoparticles,Ludox(silica),multi-walled carbon nanotubes(bamboo-shaped and hollow nanotubes)and gold,at various concentrations,were obtained using a laser Doppler electrophoresis instrument.The size of the nanoparticles on dilution was measured using dynamic light scattering(DLS).The results show that there is a concentration range within which the zeta-potential,and particle size,are not affected by nanoparticle concentration.The lower concentration limit for the system to produce consistent results was dependent on the nature of the sample under study and ranged between 10-2 and 10 4wt%.Below this concentration,there was an apparent shift in zeta-potential values to less negative values,which was accompanied by an increase in the particle size.The shift in zeta-potential was attributed to an increase in contribution of the signal from extraneous particulate matter.The increase in particle size was attributed to the nature of the homodyne optical configuration of the instrument.The aim of this study was to elucidate the range in nanopatticle concentration that allows for accurate and reliable measurement of the zeta-potential and DLS data.     

Key synthesis of magnetic Janus nanoparticles using a modified facile method

Inorganic/organic poly（methylmethacrylate-acrylic acid-divinylbenzene） iron oxide Janus magnetic nanoparticles（P（MMA-AA-DVB）/Fe3O4） with strong magnetic domains and unique surface functionalities were prepared using a solvothermal process.The P（MMA-AA-DVB） nanoparticles were prepared via soapfree emulsion polymerization and used as a precursor for preparing Janus nanoparticles.The morphology and magnetic properties of the magnetic Janus nanoparticles formed were characterized using a laser particle size analyzer,transmission electron microscopy,Fourier transform infrared spectroscopy,vibrating sample magnetometry,and thermogravimetric analysis.The synthesized P（MMA-AA-DVB）/Fe3O4 magnetic Janus nanoparticles were characterized by a Janus structure and possessed a stable asymmetric morphology after being dually functionalized.The particle size,magnetic content,and magnetic domain of the P（MMA-AA-DVB）/Fe3O4 magnetic Janus nanoparticles were 200 nm,40%,and 25 emu/g,respectively.The formation mechanism of the Janus nanoparticles was also investigated,and the results revealed that the reduction of Fe3＋ ions and growth of Fe3O4 took place on the surface of the P（MMA-AA-DVB） polymeric precursor particles.The size of the Janus particles could be controlled by narrowing the size distribution of the P（MMA-AA-DVB） precursor nanoparticles.     

NUMERICAL SIMULATION OF THE GROWTH OF NANOPARTICLES IN A FLAME CVD PROCESS

The growth of titania nanoparticles in a flame CVD process has been simulated by computational fluid dynamics, based on the change rate of particle number density due to their collisions calculated from an integral collision kernel. The assumptions made on constant particle volume density nv (nd^3), constant density of particle surface area ns (nd^2), and constant entity nd^2.5 in coagulation process have been examined. Comparisons have been made on particle size distribution between measurement results and predictions from present model of particle growth and Kruis model of particle dynamics for titania nanoparticles synthesized by the flame CVD process. Effects of operational parameters such as O2 mole fraction and particle number density on mean particle size and size distribution have been discussed.     

Backscatter phase-Doppler anemometry for transparent non-absorbing spheres

The application of phase-Doppler anemometer for scattering angles between the main rainbow and direct backscatter, was examined by calculating the spatial intensity distribution and the phase of the light scattered by a particle crossing the measuring volume. Geometrical optics was assumed and contributions to the scattered light due to reflection on the external surface of the particle and first internal reflection were considered. The response curve of the technique was calculated for different particle refractive indices, beam intersection angles, collection angles and spacings between the collection apertures. Linear response curves were obtained after integration of the intensity of the scattered light over sufficiently large rectangular collection apertures, but they became non-monotonic after a critical value of phase shift, which varied with the optical arrangement between around 220° and 360°, did not scale with common scaling parameters used for forward scatter light, and limited the possible size range of the instrument for one optical arrangement. The particle refractive index determined the collection angle and limited sizing to particles with little uncertainty in refractive index, since a 5% change in refractive index led to uncertainties in size of the order of 100%. An alternative sizing technique is suggested for the backscatter region.     

蒙特卡洛方法数值研究大气颗粒物动力学效应和辐射传输性质

爆发性增强的雾天,空气污染严重能见度低,这与大气边界层湍流性质、悬浮颗粒的动力学及散射性质密切相关.文中基于颗粒群平衡方程和Mie理论,采取加权蒙特卡洛方法,自行开发了Fortran程序.文中计算所得的颗粒尺度分布函数、颗粒散射性质与实验值、理论解一致,验证了数值模型和方法的正确性.此外,数值研究了雾爆发性增强阶段雾滴谱拓宽、能见度降低的机理,讨论湍流输运和颗粒局部聚集效应下颗粒间的碰并过程,并耦合颗粒散射性质,数值分析雾发展中湍流耗散率对颗粒对径向相对速度、系统透过率的影响;以及颗粒对径向相对速度与系统透过率、颗粒尺度的关系.研究结果表明:随着湍流耗散率的增大,颗粒的径向相对速度呈现先缓慢而后快速增大的变化趋势.1000s时刻,湍流的耗散率为1.0×10-2m2/s3,颗粒径向相对速度(无量纲)为0.0969;对于0.6μm的可见光,雾环境颗粒系统的透过率为0.47.此外,雾发展中雾滴易与气溶胶碰并,系统的散射性质与水组成的雾滴系统不同,天气的能见度明显降低.      

Detection of viscoelasticity in aggregating dilute protein solutions through dynamic light scattering-based optical microrheology

This study illustrates the applicability of dynamic light scattering (DLS)-based optical microrheology in generating new insights into the rheological response of dilute protein solutions as they start to form insoluble aggregates under the influence of a thermal stress. The technique is also shown to provide a quick method for measuring the viscosity in protein solutions. The optical microrheological technique, which is based on DLS with improved single scattering detection, is shown here to capture the rich dynamics in these systems, where traditional mechanical rheometry cannot be effectively employed due to low torque generation and high sample volume requirements and the more widely known diffusing wave spectroscopy microrheology technique is not desirable due to the required high probe particle concentrations The study illustrates the careful consideration which must be given to the tracer particle surface chemistry, tracer particle concentration and tracer particle size in order to extract out rheological responses that are truly representative of the underlying protein dynamics and microstructure. We outline a procedure for ensuring that the pitfalls inherent to this type of measurement are avoided.     

PRODUCTION OF PIGMENT NANOPARTICLES USING A WET STIRRED MILL WITH POLYMERIC MEDIA

Pigment nanoparticles with a size range of 10-100 nm were produced from large agglonmerates via a stirred media mill operating in the wet-batch mode and using polymeric media,The effects of several operating variables such as the surfactant concentration,polystyrene media loading.and media size on the pigment size distribution of the product were studied.The process dynamics was also investigated.Dynamic light scattering and electron microscopy were used as the characerization techniques.The polymeric grinding media are found to be effective for the production of pigment nanoparticles.The experimental results suggest the existence of an optimum media size and surfactant concentration,A population balance model of the process reveals a transition from first-order breakage kinetice for rela-large agglomerates split in a first-order kinetics,with a delay period,for the smaller particles.The model implies that large agglomerates split in a first-order fashion whereas the breakage of individual naoparticles may depend on induced fatigue of the particles.     

Nano-particle sizing by laser-induced-incandescence (LII) in a shock wave reactor

Abstract. Laser-Induced Incandescence (LII) is a relatively new optical diagnostic for particle sizing which is currently used in combustion science. Its advantage against light extinction and light scattering methods is the possibility of getting size information with high time and space resolution even for nano-particles. LII is mostly applied to particle formation or particle removal in reactive stationary flows, but it can also be used in shock-induced reactive flows. This is demonstrated in three examples: soot particle formation during high temperature pyrolysis of benzene, iron particle formation from iron pentacarbonyl, and formation of carbon-coated iron particles. From the principles of LII, it is not possible to obtain a complete particle growth curve from one individual shock tube experiment. Therefore, the kinetics of particle growth evolution must be determined from several “identical” shock tube experiments with a delayed triggering of the heat-up laser. The principles of LII, the in-situ measurement of particle size, and the comparison to beam-collected particles, which were visualized by a high resolution transmission electron microscope (HRTEM), are demonstrated. It was found that the energy accommodation coefficient during the particle cooling is for a soot surface but is significantly lower e.g. for an iron surface. Received 30 April 2002 / Accepted 9 December 2002 Published online 4 February 2003 Correspondence to: R. Starke (e-mail: starke@ivg.uni-duisburg.de)     

Scalable gas-phase processes to create nanostructured particles

The properties of nanoparticles are often different from those of larger grains of the same solid material because of their very large specific surface area. This enables many novel applications, but properties such as agglomeration can also hinder their potential use. By creating nanostructured particles one can take optimum benefit from the desired properties while minimizing the adverse effects. We aim at developing high-precision routes for scalable production of nanostructured particles. Two gas-phase synthesis routes are explored. The first one - covering nanoparticles with a continuous layer - is carried out using atomic layer deposition in a fluidized bed. Through fluidization, the full surface area of the nanoparticles becomes available. With this process, particles can be coated with an ultra-thin film of constant and well-tunable thickness. For the second route - attaching nanoparticles to larger particles - a novel approach using electrostatic forces is demonstrated. The micron-sized particles are charged with one polarity using tribocharging. Using electrospraying, a spray of charged nanoparticles with opposite polarity is generated. Their charge prevents agglomeration, while it enhances efficient deposition at the surface of the host particle. While the proposed processes offer good potential for scale-up, further work is needed to realize large-scale processes.     

Controllable preparation of particles with microfluidics

This paper reviews recent development and achievements in controllable preparation of nanoparticles, micron spherical and non-spherical particles, using microfluidics. A variety of synthesis strategies are presented and compared, including single-phase and multiphase microflows. The main structures of microfluidic devices and the fundamental principles of microflows for particle preparation are summarized and identified. The controllability of particle size, size distribution, crystal structure, morphology, physical and chemical properties, is examined in terms of the special features of microfluidic reactors. An outlook on opinions and predictions concerning the future development of powder technology with microfluidics is specially provided.     

In-line imaging measurements of particle size,velocity and concentration in a particulate two-phase flow

A novel method is developed for in-line measurements of particle size, velocity and concentration in a dilute, particulate two-phase flow based on trajectory image processing. The measurement system consists of a common industrial CCD camera, an inexpensive LED light and a telecentric lens. In this work, the image pre-processing steps include stitching, illumination correction, binarization, denoising, and the elimination of unreal and defocused particles. A top-hat transformation is found to be very effective for the binarization of images with non-uniform background illumination. Particle trajectories measured within a certain exposure time are used to directly obtain particle size and velocity. The particle concentration is calculated by using the statistics of recognized particles within the field of view. We validate our method by analyzing experiments in a gas-droplet cyclone separator. This in-line image processing method can significantly reduce the measurement cost and avoid the data inversion process involved in the light scattering method.     

Light scattering: A review of particle characterization applications

This review covers the progress of light scattering applications in the field of particle characterization in the past decade. The review addresses static light scattering (the measurement of scattering intensities due to light–particle interaction at various spatial locations), dynamic light scattering (the measurement of scattering due to light–particle interaction as a function of time), and scattering tracking analysis (the tracking of particle movement through scattering measurement).     

In-line imaging measurements of particle size,velocity and concentration in a particulate two-phase flow

A novel method is developed for in-line measurements of particle size, velocity and concentration in a dilute, particulate two-phase flow based on trajectory image processing. The measurement system consists of a common industrial CCD camera, an inexpensive LED light and a telecentric lens. In this work, the image pre-processing steps include stitching, illumination correction, binarization, denoising, and the elimination of unreal and defocused particles. A top-hat transformation is found to be very effective for the binarization of images with non-uniform background illumination. Particle trajectories measured within a certain exposure time are used to directly obtain particle size and velocity. The particle concentration is calculated by using the statistics of recognized particles within the field of view. We validate our method by analyzing experiments in a gas-droplet cyclone separator. This in-line image processing method can significantly reduce the measurement cost and avoid the data inversion process involved in the light scattering method.     

A derivation of the phase Doppler measurement relations for an arbitrary geometry

The phase Doppler measurement relations are derived based on geometric optics, assuming point detectors and an arbitrary system geometry. A simple calculation method is given for determining the necessary conversion factors in any particular geometry, assuming light scattering by either simple reflection or refraction. The regions of the particle surface participating in the scattering are identified as part of the analysis.     

First observations on break-up of particle agglomerates in shock waves

The destruction of solid agglomerates suspended in argon by means of shock waves (1 <M _s < 5) has been studied experimentally using a conventional shock tube apparatus. The change in particle size was measured by time-dependent in situ laser light scattering of the particle ensemble in the shock wave. The test facilities used are given in details, and the principle of the Mie-theory, necessary for complete understanding of the data reduction, is described. In this paper data reduction and first analysis employing two independent trial solutions involving the Mie-theory for polydisperse, spherical particle-ensembles are presented. Three types of agglomerates suspended in argon with a mean initial size of about 1 gm were exposed to the shock wave and different size reduction behaviours were observed. The deagglomeration effect depends largely on the wave intensity and on the physico-chemical structure of the particle aggregates.     

Ultrasonic attenuation spectroscopy for multivariate statistical process control in nanomaterial processing

Ultrasonic attenuation spectroscopy (UAS) is an attractive process analytical technology (PAT) for on-line real-time characterisation of slurries for particle size distribution (PSD) estimation. It is however only applicable to relatively low solid concentrations since existing instrument process models still cannot fully take into account the phenomena of particle–particle interaction and multiple scattering, leading to errors in PSD estimation. This paper investigates an alternative use of the raw attenuation spectra for direct multivariate statistical process control (MSPC). The UAS raw spectra were processed using principal component analysis. The selected principal components were used to derive two MSPC statistics, the Hotelling's T² and square prediction error (SPE). The method is illustrated and demonstrated by reference to a wet milling process for processing nanoparticles.     

MONODISPERSED AND NANOSIZED DENDRIMER／POLYSTYRENE LATEX PARTICLES

Emulsion polymerization of styrene was carried out using dendrimer DAB-dendr-(NH2)64 as seed. The size and size distribution of the emulsion particles were characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS), and the effects o.f emulsion polymerization conditions on the preparation of emulsion particle were investigated. It has been found that the nanosized dendrimer/polystyrene polymer emulsion particles obtained were in the range of 26～64nm in diameter, and were monodisperse; the size and size distribution of emulsion particles were influenced by the contents of dendrimer DAB-dendr-(NH2)64, emulsifier and initiator, as well as the pH value.     

Resonance scattering characteristics of double-layer spherical particles

Based on the principle of ultrasonic resonance scattering, sound-scattering characteristics of double-layer spherical particles in water were numerically studied in this paper. By solving the equations of the scattering matrix, the scattering coefficient determined by the boundary conditions can be obtained, thus the expression for the sound-scattering function of a single double-layer spherical particle can be derived. To describe the resonance scattering characteristics of a single particle, the reduced scattering cross section and reduced extinction cross section curves were found through numerical calculation. Similarly, the numerically calculated sound attenuation coefficient curves were used to depict the resonance scattering characteristics of monodisperse and polydisperse particles. The results of numerical calculation showed that, for monodisperse particles, the strength of the resonance was mainly related to the particle size and the total number of particles; while for polydisperse particles, it was primarily affected by the particle size, the coverage of the particle size distribution and the particle concentration.