Multimethod 3D characterization of natural plate-like nanoparticles: shape effects on equivalent size measurements

The fundamental properties and processes that govern nanoparticle behavior in colloidal dispersions are critical to predict their performance in applications and also their environmental and health implications. Illite is a platy clay mineral that is present in large amounts in aquatic environments and can be used as a model natural particle for environmental risk assessment. However, the high-aspect ratio of illite makes conventional analysis, usually assuming a spherical size, insufficient for the assessment of shape-dependent properties. In the current paper, a multimethod characterization of a suspension of illite particles was done using atomic force microscopy, scanning electron microscopy, dynamic light scattering (DLS), nanoparticle tracking analysis, differential centrifugal sedimentation, and centrifugal-field flow fractionation coupled to multiangle light scattering and DLS. The relation between the different measurands was investigated, and the effect of the shape on the equivalent particle size was reported. While some of the used techniques are capable of assessing the aspect ratio of illite, the results confirm the need for multiple techniques and analysis of different types of measurands especially for high-aspect-ratio particles.     

Dynamic Light Scattering Measurement of Nanometer Particles in Liquids

Dynamic light scattering (DLS) techniques for studying sizes and shapes of nanoparticles in liquids are reviewed. In photon correlation spectroscopy (PCS), the time fluctuations in the intensity of light scattered by the particle dispersion are monitored. For dilute dispersions of spherical nanoparticles, the decay rate of the time autocorrelation function of these intensity fluctuations is used to directly measure the particle translational diffusion coefficient, which is in turn related to the particle hydrodynamic radius. For a spherical particle, the hydrodynamic radius is essentially the same as the geometric particle radius (including any possible solvation layers). PCS is one of the most commonly used methods for measuring radii of submicron size particles in liquid dispersions. Depolarized Fabry-Perot interferometry (FPI) is a less common dynamic light scattering technique that is applicable to optically anisotropic nanoparticles. In FPI the frequency broadening of laser light scattered by the particles is analyzed. This broadening is proportional to the particle rotational diffusion coefficient, which is in turn related to the particle dimensions. The translational diffusion coefficient measured by PCS and the rotational diffusion coefficient measured by depolarized FPI may be combined to obtain the dimensions of non-spherical particles. DLS studies of liquid dispersions of nanometer-sized oligonucleotides in a water-based buffer are used as examples.     

对利用动态光散射法测量颗粒粒径和液体黏度的改进

光散射技术通过测量悬浮液中布朗运动颗粒的平移扩散系数,得到颗粒流体力学直径或液体黏度.本文由单参数模型入手,建立了低颗粒浓度下,单颗粒平移扩散系数与颗粒集体平移扩散系数和颗粒浓度之间的线性依存关系并将其引入光散射法中,从而对现有的测量方法进行了改进.改进后的测量方法可实现纳米尺度球型颗粒标称直径的测量和液体黏度的绝对法测量.以聚苯乙烯颗粒+水和二氧化硅颗粒+乙醇两个分散系为参考样本,通过实验,验证了改进后方法的可行性.此外,还针对上述两个分散系,实验探讨了温度和颗粒浓度对颗粒集体平移扩散系数的影响规律,发现聚苯乙烯颗粒+水分散系中,颗粒间相互作用表现为引力;二氧化硅颗粒+乙醇分散系中,颗粒间相互作用表现为斥力.讨论了颗粒集体平移扩散系数随颗粒浓度变化规律与第二渗透维里系数的关系.     

A comparison of atomic force microscopy (AFM) and dynamic light scattering (DLS) methods to characterize nanoparticle size distributions

This paper compares the accuracy of conventional dynamic light scattering (DLS) and atomic force microscopy (AFM) for characterizing size distributions of polystyrene nanoparticles in the size range of 20–100 nm. Average DLS values for monosize dispersed particles are slightly higher than the nominal values whereas AFM values were slightly lower than nominal values. Bimodal distributions were easily identified with AFM, but DLS results were skewed toward larger particles. AFM characterization of nanoparticles using automated analysis software provides an accurate and rapid analysis for nanoparticle characterization and has advantages over DLS for non-monodispersed solutions.     

Polydisperse spherical colloidal silica particles:Preparation and application

A new industrial method has been developed to produce polydisperse spherical colloidal silica particles with a very broad particle size,ranging from 20-95 nm.The process uses a reactor in which the original seed solution is heated to 100 ℃,and then active silicic acid and the seed solution are titrated to the reactor continuously with a constant rate.The original seeds and the titrated seeds in the reactor will go through different particle growth cycles to form different particle sizes.Both the particles' size distribution and morphology have been characterized by dynamic light scattering(DLS)and the focus ion beam(FIB) system.In addition,the as-prepared polydisperse colloidal silica particle in the application of sapphire wafer's chemical mechanical polishing(CMP) process has been tested.The material removal rate(MRR) of this kind of abrasive has been tested and verified to be much faster than traditional monodisperse silica particles.Finally,the mechanism of sapphire CMP process by this kind of polydisperse silica particles has been investigated to explore the reasons for the high polishing rate.     

Colloidal Analysis of Particles Extracted from Microalloyed Steels

Different colloidal particle characterization methods are examined for their suitability to determine the particle size distribution of particles extracted from steels. Microalloyed steels are dissolved to extract niobium and titanium carbonitride particles that are important for the mechanical properties of these steels. Such particles have sizes ranging from several nanometers to hundreds of nanometers depending on the precipitation stage during the thermomechanically controlled rolling process. The size distribution of the particles is analyzed by dynamic light scattering (DLS), analytical ultracentrifugation (AUC), and hollow fiber flow field-flow fractionation (HF5) and compared to data obtained for reference particles as well as data from electron microscopy, the standard sizing technique used in metallurgy today. AUC and HF5 provide high-quality size distributions, average over large particle numbers that enables statistical analysis, and yield useful insights for alloy design; however, DLS fails due to a lack of resolution. Important aspects in the conversion and comparison of size distributions obtained for broadly distributed particle systems with different measurement principles and the role of surfactants used in sample preparation are discussed.     

动态光散射和透射电镜法研究pH和NaCl对 丝胶蛋白微观结构的影响

应用近红外光谱法、动态光散射法及透射电镜扫描法,研究了pH和NaCl浓度对丝胶蛋白聚集微观结构的影响。近红外光谱显示丝胶蛋白在酰氨Ⅰ带1 700～1 600 cm-1附近有较强吸收峰。通过zeta电势法测定丝胶蛋白的表观等电点为pH 3.7。应用动态光散射法测定了在不同pH和NaCl浓度下丝胶蛋白颗粒的分散粒径,pH 4及高NaCl浓度时,丝胶蛋白聚集颗粒粒径大且分散系数大;pH 3或pH 8及低NaCl浓度时丝胶蛋白聚集颗粒粒径和分散系数相对较小。采用透射扫描电镜观察丝胶蛋白在pH 3或pH 8条件下聚集形成松散的松针状微观结构,在pH 4或者高NaCl浓度下会聚集形成相对紧密的微观结构。pH 4时可以观察到丝胶蛋白的椭圆形单聚体大小约为(60±6)nm(n=10)。并探讨了静电斥力、氢键和范德华吸引力对丝胶蛋白微观结构形成的影响,为丝胶蛋白作为生物材料的应用提供了理论依据。     

随机取向群聚椭球粒子光散射特性研究

利用离散偶极子近似方法,考虑单元粒子之间的电磁相互作用,数值计算了随机取向的不同尺度参数、不同纵横比的群聚椭球粒子的缪勒矩阵元素,给出了各个缪勒矩阵元素的角分布曲线,探讨了随机取向的群聚椭球粒子的尺度参数、纵横比、基本粒子相对位置对其缪勒矩阵元素的影响。并将随机取向群聚椭球粒子的光散射特性与单个等效球形粒子的数值结果进行了比较。结果表明,随机取向群聚椭球粒子的光散射特性与等效球形粒子的光散射特性存在很大差别,基本粒子的形状越偏离球形,这种差别就越大; 随机取向群聚椭球粒子中椭球粒子的纵横比和相对位置对整个群聚粒子的缪勒矩阵元素存在不同程度的影响,并且此影响随着粒子尺度参数的增大而变得更加显著。     

随机取向群聚椭球粒子光散射特性研究

利用离散偶极子近似方法,考虑单元粒子之间的电磁相互作用,数值计算了随机取向的不同尺度参数、不同纵横比的群聚椭球粒子的缪勒矩阵元素,给出了各个缪勒矩阵元素的角分布曲线,探讨了随机取向的群聚椭球粒子的尺度参数、纵横比、基本粒子相对位置对其缪勒矩阵元素的影响。并将随机取向群聚椭球粒子的光散射特性与单个等效球形粒子的数值结果进行了比较。结果表明,随机取向群聚椭球粒子的光散射特性与等效球形粒子的光散射特性存在很大差别,基本粒子的形状越偏离球形,这种差别就越大; 随机取向群聚椭球粒子中椭球粒子的纵横比和相对位置对整个群聚粒子的缪勒矩阵元素存在不同程度的影响,并且此影响随着粒子尺度参数的增大而变得更加显著。     

The influence of filler modification on its aggregation and dispersion behaviour in silica/PBT composite

In this work, highly dispersed silica is obtained using a precipitation technique from emulsion medium. The selected emulsifier, applied in the process, allows production of silica with almost ideally spherical particles. To examine the tendency to aggregation, the silica powder is treated with commercially available silane coupling agents: 3-mercaptopropyltrimethoxysilane (A-189), N-2-(aminoethyl)-3-aminopropyltrimethoxy silane (A-1120) and 3-methacryloxypropyltrimethoxysilane (A-174). The silica microstructure is characterised by scanning electron microscopy (SEM). Size distribution of primary particles, aggregates and agglomerates structures is determined using dynamic light scattering (DLS) method. Surface treatment of silica generally enhances powder dispersibility. The pristine spherical silica and silica modified with silanes are introduced to poly(butylene terphthalate) (PBT). Dispersion of nanosize precipitated silica particles in PBT matrix is studied by SEM technique. For the visualisation of silica particles covered by polymer layer, the composite fracture surfaces are etched by air-plasma. The agglomerates of untreated silica are not efficiently destroyed during the extrusion process, whereas surface treatment by selected silanes leads to a significant reduction of agglomerate number. However, a large number of small, strongly bonded aggregates still occupied the composite structure.