Determination of Particle Size Distribution by Laser Diffraction of Doped‐CeO2 Powder Suspensions: Effect of Suspension Stability and Sonication

The particle size distributions (PSDs) of metal oxide powders are often determined by analyzing suspensions of powders using laser diffraction (e.g. Malvern MasterSizer 2000). Particle agglomeration can effectively bias the resulting distribution towards “unrealistic” particle sizes. Solutions to avoid this problem must be found if a particle distribution based on the elemental or primary particle sizes is desired. In this work, the particle size distribution of doped‐CeO₂ powders was studied. These powders show a crystalline single phase structure of controlled stoichiometry as determined by X‐ray diffraction and ICP analysis. The apparent size distribution was found to be a strong function of suspension stability. Dispersant agents (PBTCA and phosphonoacetic acid) and suspension pH affected stability as characterized by zeta potential measurements. Sonication of the suspensions further enhanced particle de‐agglomeration. Finally, only the combined effect of a dispersant agent, pH adjustment of the suspension and sonication provided a primary particle size distribution. The results presented in this work can be used in the analysis of similar ceramic powders in which strong particle agglomeration is present.     

Crystal Shape Characterisation of Dry Samples using Microscopic and Dynamic Image Analysis

A standard method to determine particle shape and size is by image analysis. This paper addresses microscopic image analysis (semi‐automated) investigations of two different organic crystalline chemicals generated by batch cooling crystallisation. The results generated from microscopic image analysis were compared with data obtained by dynamic image analysis (automated) because very few contributions are available in the open literature. The chemical systems were polymorphic L‐glutamic acid which crystallises into α (prismatic) or β (needle) form and the non‐polymorphic mono sodium glutamate which crystallises into needles. The images from these techniques were processed to generate information on crystal shape and size. It has been observed that shape effects can distort the size obtained in size characterization studies. In this study, comparisons were made of processing time, number of crystals and accuracy between microscopic and dynamic image analysis. For representative microscopic image analysis, 5000 crystals were analysed in an average of eight hours while several hundred thousand crystals were processed using dynamic image analysis within 15 minutes. Using the parameters D₁₀, D₅₀, D₉₀, span and aspect ratio for statistical comparison, it was found that the results obtained for D₅₀ by the two techniques were comparable and in accordance with other measurements (laser diffraction spectroscopy and ultrasonic attenuation spectroscopy) even though these non‐spherical particles had different orientations during measurement by the two methods. However, substantial differences in span of the distribution and aspect ratio were returned by the two techniques.     

沉淀法制备超细氧化铝粉末过程中的团聚机理和消除办法

采用沉淀法以Al(NO3)3.9H2O和NH3.H2O为原料制备了Al(OH)3干凝胶,经过高温煅烧合成纳米级的α-Al2O3粉末,分析了在制备过程中氧化铝粉末产生团聚的机理,推测了硬团聚的机理模型,并提出了几种消除硬团聚的方法,制备出的α-Al2O3粉末,粒径分布均匀,且无明显团聚,近似球形,平均粒径为70nm。     

Pulsed laser induced synthesis of scheelite-type colloidal nanoparticles in liquid and the size distribution by nanoparticle tracking analysis

Pulsed laser ablation (PLA) of ceramic target in liquid phase was successfully employed to prepare calcium tungstate (CaWO₄) and calcium molybdate (CaMoO₄) colloidal nanoparticles. The crystalline phase, particle morphology and optical property of the colloidal nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy. The produced stable colloidal suspensions consisted of the well-dispersed nanoparticles showing a spherical shape. The mechanism for the laser ablation and nanoparticle forming was discussed under consideration of photo-ablation process. Nanoparticle tracking analysis using optical microscope combined with image analysis was proposed to determine the size distribution function of the prepared colloidal nanoparticles. The mean size of the CaWO₄ and CaMoO₄ colloidal nanoparticles were 16 and 29 nm, with a standard deviations of 2.1 and 5.2 nm, respectively.     

In-Line Particle Size Determination for Jet Agglomeration Processes

In jet agglomeration plants, powders are agglomerated to obtain good instant properties. The free-falling initial material is wetted in a spray cone by droplets or in a steam jet by condensation at the particle surface. In a subsequent region of high particle concentration, collision between particles occurs and agglomerates form, if the forces of adhesion are strong enough. A commercial measurement device, working according to the principle of Fraunhofer diffraction, was modified for in-line application. It was used to measure particle size distributions and concentrations of solid particles and droplets in jets. A model is presented to calculate local particle sizes by means of mass balances from integral measurements over large volumes. The results of in-line particle size and agglomerate size analyses show the practical importance of dry agglomeration during transport and lead to a better understanding of the subsequent wet agglomeration process.     

Sedimentation Image Analysis (SIA) for the Simultaneous Determination of Particle Mass Density and Particle Size

A new method for the simultaneous determination of the distribution of particle mass density and the distribution of particle size with a technique with only a single measurement is presented. The basic idea of the new optical method is the analysis of gravitational particle settling by a digital image acquisition system. Individual particles illuminated by a laser light sheet are tracked by a continuously operating CCD camera. The projected area, shape factors and the centre of gravity are detected during the sedimentation process from a series of images with a constant time spread. As the algorithm is based on single particle tracking, the heterogeneity of the sample can be taken into account. From these measured particle characteristics, particle size and settling rate are calculated. Thus particle mass density is obtained taking into account also the influence of particle shape on the settling process. This method, which we name sedimentation image analysis (SIA), is particularly suitable for the characterization of heterogeneous material, e.g. soil, in the micrometer range.     

非球形椭球粒子参数变化对光偏振特性的影响

针对自然界中多数沙尘、烟煤粒子的非球形问题, 在球形粒子偏振特性的基础上, 进一步研究非球形椭球粒子的折射率、有效半径、粒子形状等参数变化对光偏振特性的影响, 采用基于T矩阵的非球形粒子仿真方法, 模拟非偏振光经椭球粒子传输后光的偏振特性及其与球形粒子间的差异, 并以实际沙尘、海洋、烟煤三种气溶胶粒子为例说明结果的正确性. 结果表明: 当折射率实部越小, 虚部越大时, 球形粒子与非球形粒子的偏振差异越不明显; 当粒子有效半径增加时, 球形粒子偏振度的变化比非球形粒子更为明显, 且最大值分别出现在散射角为150°和120°的位置; 当粒子形状不同时, 不同形状椭球及球形粒子的差异在散射角小于60° 时并不明显, 且当椭球粒子纵横比互为倒数时, 两种粒子的偏振特性近似相同. 通过以上分析可知, 在光传输过程中, 椭球粒子多数情况下无法被近似为球形粒子进行计算.     

Droplet Size Distribution and Sphericity Measurements of Low‐Density Sprays Through Image Analysis

An image analysis technique has been developed in order to determine the drop size distributions of sprays produced by low‐velocity plain cylindrical jets. The particle sizing method is based on incoherent backlight images. Each drop is analyzed individually in the image. The two‐dimensional image resulting from the projection of the three‐dimensional object shape (the drop) on a screen (the video sensor surface) is modeled. The model, based on the point spread function formulation, has been developed to derive a relation between contrast and relative width of individual drops. This relation is used to extend the domain of validity of drop size in terms of size range, out of focus and image resolution. The shape parameter is determined for each drop image through morphological analysis. Spherical and non‐spherical droplets are then sorted on the basis of this parameter. Non‐spherical drops are regarded as non‐fully atomized liquid bulks or coalesced drops. Finally, the droplet size distribution of true spherical droplets is established for a low‐velocity plain cylindrical liquid jet.     

Evolution of terahertz conductivity in ZnSe nanocrystal investigated with optical-pump terahertz-probe spectroscopy

The unique optical properties of nanoparticles are highly sensitive in respect to particle shapes, sizes, and localization on a sample. This demands for a fully controlled fabrication process. The use of femtosecond laser pulses to generate and transfer nanoparticles from a bulk target towards a collector substrate is a promising approach. This process allows a controlled fabrication of spherical nanoparticles with a very smooth surface. Several process parameters can be varied to achieve the desired nanoparticle characteristics. In this paper, the influence of two of these parameters, i.e. the applied pulse energy and the laser beam shape, on the generation of Si nanoparticles from a bulk Si target are studied in detail. By changing the laser intensity distribution on the target surface one can influence the dynamics of molten material inducing its flow to the edges or to the center of the focal spot. Due to this dynamics of molten material, a single femtosecond laser pulse with a Gaussian beam shape generates multiple spherical nanoparticles from a bulk Si target. The statistical properties of this process, with respect to number of generated nanoparticles and laser pulse energy are investigated. We demonstrate for the first time that a ring-shaped intensity distribution on the target surface results in the generation of a single silicon nanoparticle with a controllable size. Furthermore, the generated silicon nanoparticles presented in this paper show strong electric and magnetic dipole resonances in the visible and near-infrared spectral range. Theoretical simulations as well as optical scattering measurements of single silicon nanoparticles are discussed and compared.     

Particle size analysis: A comparison of various methods ii

In previous work, the relative performance of various methods used to characterize the particle size distribution of powders composed of fine irregularly shaped particles was assessed. It was found that methods employing Fraunhofer diffraction theory were inferior with respect to particle counting methods. Furthermore, calculated particle size distributions varied considerably between manufactures of Fraunhofer devices. It is well known that the Mie optical model can also be used to analyze the data collected by laser diffraction instruments. Here, we have compared particle size distributions collected using two Laser diffraction instruments to those determined by the Aerosizer. In our earlier work the Aerosizer was shown to produce results nearly identical to those determined by image analysis. The results of this study indicate that the use of the Mie optical model does not correct for deficiencies previously noted for laser diffraction methods. Considerable variation exists between the results obtained on laser diffraction instruments manufactured by different companies. Our earlier recommendation to use extreme caution when employing laser diffraction instruments to characterize fine powders continues to be supported in the present work.     

Technical Note: Powder Production by Gas Atomization of Bioglass Melt

Bioglass melts are granulated by hot gas atomization techniques, where spherical powder and fiber type products are respectively available depending on different process parameters. Higher atomization gas temperatures induce higher powder fractions, while at ambient gas temperature fiber materials can be produced. The diameter of the as‐atomized fiber material decreases with increasing melt temperature. Particle size analysis, Scanning Electron Microscopy, and optical observation of the atomized materials are performed. The melt disintegration mechanism and the particle shape and size dependency on process parameters are discussed.     

Using In Situ Image Analysis to Study the Kinetics of Agglomeration in Suspension

Agglomeration in suspension is a size‐enlargement method which allows the formation of spherical agglomerates of a few millimeters from fine particles (<100μm) by the action of a binding liquid. This paper proposes a new technique to measure the particle size distribution in order to determine agglomeration kinetics. The device, which consists of a video camera focused on a black flat screen fixed inside the crystallizer and connected to an image analysis system, films and measures in situ the particles circulating between the screen and the transparent crystallizer wall. This visual method also gives an interesting insight into agglomeration mechanisms.     

Synthesis of nanocrystalline titania in pure water by pulsed Nd:YAG Laser

Synthesis of titania (TiO₂) nanoparticles (NPs) has been performed with pulsed laser ablation (PLA) approach by irradiating a 1064 nm Nd:YAG laser pulses on the titanium target immersed in pure water. A systematic characterization on the products, synthesized in different laser pulse energies, illustrated the conspicuous dependence of crystalline phase and size distribution of the NPs on this parameter. Emission spectroscopy of the induced plasma was exploited to justify the formation of titania NPs through the synthesis process, as well as the emergence of rutile phase beside the anatase by increasing the laser pulse energies. In addition, UV-vis optical absorption and Raman spectroscopy, associated with X-ray diffraction (XRD) were employed to quantitatively determine the crystalline phases of the products. Morphological observations by means of transmission electron microscopy (TEM), demonstrating the spherical shape of the synthesized NPs, was utilized to investigate the variation of particle size distribution with the laser pulse energy.     

Fabrication of copper oxide nanofluid using submerged arc nanoparticle synthesis system (SANSS)

The optimal parameters are found for preparing nanofluid in our submerged arc nanoparticle synthesis system (SANSS) using a copper electrode. A suspended copper oxide nanofluid is thus produced at the current of 8.5–10 A, voltage of 220 V, pulse duration of 12 μs, and dielectric liquid temperature of 2°C. The CuO nanoparticle are characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), electron diffraction pattern (SAD) and electron spectroscopy for chemical analysis (ESCA). The equality volume spherical diameter of the obtained copper oxide particle is 49.1 nm, regular shape and narrow size distribution.This revised version was published online in August 2005 with a corrected issue number.     

Fabrication of copper oxide nanofluid using submerged arc nanoparticle synthesis system (SANSS)

The optimal parameters are found for preparing nanofluid in our submerged arc nanoparticle synthesis system (SANSS) using a copper electrode. A suspended copper oxide nanofluid is thus produced at the current of 8.5–10 A, voltage of 220 V, pulse duration of 12 μs, and dielectric liquid temperature of 2°C. The CuO nanoparticle are characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), electron diffraction pattern (SAD) and electron spectroscopy for chemical analysis (ESCA). The equality volume spherical diameter of the obtained copper oxide particle is 49.1 nm, regular shape and narrow size distribution.     

The Effect of Boundary Conditions on Gas-phase Synthesised Silver Nanoparticles

We have prepared spherical non-agglomerated silver nanoparticles by an evaporation–condensation–dilution/cooling technique. Silver was evaporated from a crucible in a tubular flow reactor. A porous tube diluter was used to quench the carrier gas at the outlet of the reactor to enhance the formation of small particles and to suppress agglomeration and other particle growth mechanisms. The number size distribution of the prepared particles was measured with a differential mobility analyser–condensation nucleus counter combination and the size and the shape of the particles were analysed with transmission electron microscope. The system was modelled using a sectional aerosol dynamics computer code to estimate the importance of different aerosol processes. In all conditions the particles obtained were non-agglomerated and spherical. The mean particle diameter varied from 4 to 10-nm depending on boundary conditions. From the modelling studies it can be concluded that the nucleation rate is the most important parameter controlling the final particle size.     

Intensity of optical field inside a weakly absorbing spherical particle irradiated by a femtosecond laser pulse

Using the Fourier technique in combination with the Mie theory, we study numerically the spatiotemporal evolution of the intensity of the internal optical field inside micron-sized weakly absorbing spherical particles upon diffraction by these particles of a femtosecond laser field. A number of specific features of the dynamics of the spatial intensity distribution of the femtosecond pulses inside the particles are found to depend on the pulse width, the shape of the laser beam, the size of the particles, and the geometry of their irradiation. It is shown that, under conditions of nonstationary diffraction, the internal optical field is usually excited in a resonance way, with the eigenfrequencies of one or several high-Q resonance modes of the particle falling into the central part of the original pulse spectrum. This causes a time delay of the light in the particle and a reduction of the absolute maximum in the time dependence of the internal field intensity as compared with a stationary regime. The greatest reduction of the peak occurs at exact resonance. In this case, the decrease in the peak intensity may reach several orders of magnitude. Irradiation of a particle by a narrow Gaussian beam of femtosecond duration directed toward the particle center enhances the internal field intensity as compared with the case of near-edge incidence.     

Size Determination of Au Aerosol Nanoparticles by Off-Line TEM/STEM Observations

Determination of particle size distributions of Au aerosol nanoparticles has been performed by a TEM/STEM investigation. The particles are generated by an evaporation/condensation method and are size-selected by differential mobility analyzers (DMA) based on their electrical mobility. Off-line TEM measurements resulted in equivalent projected area diameters assuming that the particles are spherical in shape. In this paper critical factors such as magnification calibration, sampling, image analysis, beam exposure and, particle shape are treated. The study shows that the measures of central tendency; mean, median and mode, are equal as expected from a narrow size distribution. Moreover, the correlation between TEM/STEM and DMA are good, in practice 1:1. Also, STEM has the advantage over TEM due to enhanced contrast and is proposed as an alternative route for determination of particle size distributions of nanoparticles with lower contrast.     

Determination of Particle Size Distribution by Par-Tec® 100: Modeling and Experimental Results

Some particle size analyzers, such as the Par-Tec® 100 (Laser Sensor Technology, Redmond, WA, USA), measure the so-called cord length distribution (CLD) as the laser beam emitted from the sensor randomly crosses two edges of a particle (a cord length). The objectives of this study were to develop a model that can predict the response of the Par-Tec® 100 in measuring the CLD of a suspension for spherical and ellipsoidal particles and to infer the actual particle size distribution (PSD) using the measured CLD output. The model showed that the measured CLD is reasonably accurate for the spherical particles. However, this measurement progressively deteriorates as the shape of particles changes from spherical to ellipsoidal with large ratios of major to minor diameters. Experimental results obtained with spherical particles having a normal and a non-normal PSD indicated that the Par-Tec® 100 measurements deteriorate as the PSD deviates from a normal distribution. The information obtained from these experiments also showed that the model can reasonably predict the Par-Tec® response. Use of the inferred PSD rather than the measured CLD made a major improvement in estimating the actual PSD. Mean particle size analysis revealed that the Par-Tec® 100 volume-weighted mean particle size is closest to the unweighted mean particle size measured by sieve analysis.