Reflection Phenomena in Particle Sizing by static and dynamic light scattering

Using a monodisperse poly(methyl methacrylate) dispersion it was shown that light reflection at the sample cuvette walls may greatly influence the results of both static (SLS) and dynamic (DLS) light scattering experiments. Considering SLS, this reflection phenomenon mostly causes an overestimation of the scattered intensity at high scattering angles, which may give rise to the emergence of an additional, artificial peak in the lower region of the particle size distribution. On the other hand, the influence of reflection on DLS experiments was shown to be particularly important in the upper region of the particle size distribution. The experimentally observed phenomena were explained from basic principles of both particle sizing methods. Finally, it was shown that the disturbing effect of reflection could be avoided by modifying either the hardware or the software of the SLS and DLS techniques.     

Temperature-sensitive poly(N-Isopropyl-Acrylamide) microgel particles: A light scattering study

We present a light scattering study of aqueous suspensions of microgel particles consisting of poly(N-Isopropyl-Acrylamide) cross-linked gels. The solvent quality for the particles depends on temperature and thus allows tuning of the particle size. The particle synthesis parameters are chosen such that the resulting high surface charge of the particles prevents aggregation even in the maximally collapsed state. We present results on static and dynamic light scattering (SLS/DLS) for a highly diluted sample and for diffuse optical transmission on a more concentrated system. In the maximally collapsed state the scattering properties are well described by Mie theory for homogenous hard spheres. Upon swelling we find that a radially inhomogeneous density profile develops.     

光散射聚集速率测定中T矩阵方法的应用

聚集速率是评估胶体体系特性及稳定性的关键参数, 静态光散射和动态光散射则是测量聚集速率的两个重要方法. 然而, 用静态光散射和动态光散射测量聚集速率时, 需要知道有关单粒子和双粒子聚集体光散射特性的数据. 为此, 通常需要把动、静两种方法结合, 才能消去这个数据. 以前各种近似理论曾用来解决这个问题, 但因粒子尺寸和形状的限制, 结果并不理想. 而T矩阵方法可以不受粒子大小和形状的限制计算其光散射特性. 本工作用T矩阵方法直接计算静态光散射和动态光散射所必须的粒子散射特性, 并将该法得到的聚集速率与动静态光散射结合法得到的聚集速率进行了比较, 两者结果很接近. 本工作为简化静态光散射和动态光散射测量聚集速率, 扩展其应用范围开辟了新途径. 关键词： T矩阵')" href="#">T矩阵 光散射法 聚集速率     

Swelling/deswelling of polyacrylamide gels in aqueous NaCl solution: Light scattering and macroscopic swelling study

Swelling kinetics of water-swollen polyacrylamide (PAAm) hydrogels (WSG) was investigated in various concentrations of aqueous NaCl by macroscopic swelling measurements. For lower concentration of NaCl, WSG showed exponential swelling whereas at higher concentration of NaCl it underwent deswelling at short times and exponential swelling at long times. From these studies, collective diffusion coefficient, D, of the polymer network and polymer?Csolvent interaction parameter, ??, were calculated and found to decrease with increase in [NaCl]. Collective diffusion coefficients measured from dynamic light scattering (DLS) and that obtained from macroscopic swelling measurements are found to agree well. Measured ensemble-averaged dynamic structure factor f(q,t) for WSG and salt-swollen gels (SSG) showed an initial decay followed by a plateau at long times and it can be described by harmonically bound Brownian particle (HBBP) model. Enhanced scattering intensity at low scattering angles using static light scattering (SLS) measurements revealed the presence of inhomogeneities in PAAm gels. The reasons for increased scattering intensity of SSG over WSG gel and the linear decrease of D with increase in NaCl concentration are explained.     

动态光散射测量粒径分布的格雷码编码遗传算法反演运算

采用格雷码编码的遗传算法对动态光散射测量的粒径分布进行反演运算,数字测试结果表明,对于无噪声的分布,算法能精确的反演出各种粒子分布图像;对于加了一定噪声的分布,算法显示出较好的稳定性,能反演出主峰的分布图像.聚苯乙烯乳球的实验结果表明,该算法能反演双分布的粒径分布图像.与标准遗传算法和反演蒙特卡罗算法相比,该算法具有较高的搜索效率,能够用较少的计算时间快速搜索到最优解.格雷码编码遗传算法是一种更有效的随机反演算法.     

Particle Size Characterization of an Extra Fine Milled Product

The present research aims to characterize the particle size distribution of sub micron particles suspended in a liquid. The particles milled are an organic poorly water soluble crystalline product. To characterize the size of these particles, different techniques have been tested: imaging techniques (SEM, CryoTEM), static light scattering techniques, dynamic light scattering techniques, centrifugation and flow field flow fractionation. The results indicate that the studied milled particles have a primary particle size close to 180nm and there is strong evidence of larger particles which are very likely aggregates. This is clearly seen from the Cryo TEM results. All the above mentioned techniques should in principle be able to measure samples of dispersion containing particles of ca 180 nm but several are disturbed by the presence of large aggregates. It is difficult to estimate the amount of aggregate present, but most of the time one is interested in what the primary particle size distribution is. It is clear that no single piece of equipment is capable of exactly determining the particle size distribution of our samples, but the static light scattering with low shear on mixing does give a good representation of what is seen with the image analysis by cryo TEM.     

一种高度枝化的聚脂纳米微粒的合成与光散射表征

一种高度枝化的聚脂纳米微粒的合成与光散射表征马荣久，周博，沈家骢，吴奇，吴加辉，陈锦幌（吉林大学高分子研究所长春１３００２３香港中文大学化学系）ＳｙｎｔｈｅｓｉｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＡＮｏｖｅｌＨｉｇｈｌｙＢｒａｎｃｈｅｄＰｏｌ...     

双峰分布颗粒体系的多角度动态光散射数据反演

采用多角度动态光散射和加权正则化反演方法,对4组模拟的双峰分布颗粒体系(100/600 nm,200/600 nm,300/600 nm和350/600 nm)分别选取1、3、6和10个散射角进行测量.粒度反演结果表明,采用加权正则化方法反演双峰颗粒体系的多角度动态光散射测量数据,可获得峰值位置比小于2∶1且含有大粒径(＞350 nm)颗粒的双峰颗粒粒度分布.采用标准聚苯乙烯乳胶颗粒进行实测的结果验证了这一结论.得到含大粒径颗粒的双峰粒度分布反演结果的原因在于,多角度动态光散射能提供更多的大粒径颗粒的粒度信息,加权正则化反演方法能减少测量数据中的噪声,因而多角度动态光散射测量数据的加权反演能实现峰值位置比小于2∶1且含有大粒径颗粒的双峰颗粒体系的测量.     

Characterization of Nanoparticles by Scattering Techniques

Basic principles and applications of different scattering techniques (including static and dynamic light scattering (SLS and DLS), small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD) and small-angle neutron scattering (SANS)) on the characterization of nanoparticles are reviewed in this paper. By choosing a suitable scattering technique or a combination of different techniques for nanoparticle characterization, the particles' molecular weight, radius of gyration, hydrodynamic radius, size distribution, shape and internal structure as well as interparticle interactions of nanoparticles, can be determined. Examples including some sophisticated colloidal systems are presented.     

Comparative Test of Methods to Determine Particle Size and Particle Size Distribution in the Submicron Range

Among the most important characteristic properties of disperse systems such as latices, pigments, ceramic materials or drug formulations are the particle size and the particle size distribution. To measure these quantities, several methods and measuring instruments based on different physical principles are available. These include turbidimetry, dynamic and static light scattering, electron microscopy with image analysis, ultra- and disc centrifugation, light diffraction and the electrical sensing zone method. All these measuring techniques are doubtless necessary because of the large product variety and the broad particle size range. However, some problems arise if different techniques are used and the results are compared uncritically without considering to the application range and the resolution of the methods. An extensive comparative test was therefore carried out using seven latices in the submicron range with defined monomodal, bimodal and hexamodal particle size distributions. The most important methods of determining average particle size values and particle size distributions were tested and compared. Of the methods to determine only average particle sizes, turbidimetry is the most efficient, followed by dynamic light scattering with cumulants evaluation. Static light scattering only yields accurate results for small particles with narrow particle size distributions. Of the methods to determine particle size distributions, ultracentrifugation and, somewhat less, disc centrifugation and electron microscopy with image analysis are the most efficient. Dynamic light scattering only yields reliable results in the case of small particles with narrow distribution curves. Light diffraction and the electrical sensing zone method are less suitable for the submicron range.     

基于后向散射的高浓度纳米颗粒粒度分布测量方法研究

传统的动态光散射法通常采集侧向散射进行纳米颗粒粒度分布的测量,由于多次散射的影响,利用侧向散射不能准确测量高浓度样品的颗粒粒度分布。针对该问题,对后向散射测量方法进行了研究,在实验基础上提出了后向散射最佳光程的判断准则。在不同样品浓度下,用侧向散射和后向散射方法对标称粒径分别为110 nm、220 nm的聚苯乙烯乳胶球颗粒进行了测量。实验结果表明,对于高浓度的待测样品,后向散射测量方法通过自适应调整光程,在最优光程处进行测量,能够有效得到高浓度纳米颗粒的粒径及粒度分布,测量结果相对误差为2.72%。     

Particle Manipulation by Ultrasonic Standing Wave Fields to complement dynamic light scattering experiments

Dynamic light scattering is a widely used technique for the sizing of colloidal suspensions. It is capable of measuring particles across the size range from approximately 1 nm to several microns. However the larger particle sizes tend to pose problems for the interpretation of the scattered light signal either by virtue of their light scattering efficiency relative to the smaller species present or the departure of the scattered light signal from Gaussian statistics. Rapid removal of such particles in-situ could extend the use of dynamic light scattering particularly in on-line analysis or laboratory automated measurement. In this paper a method is demonstrated for the in-situ removal of larger particles in suspension by means of ultrasonic standing waves and concurrent dynamic light scattering measurement. The theory behind ultrasonic particle manipulation and its effect on the motion of the particles is discussed. Data from a scattering cell designed to incorporate the ultrasonic technology is presented showing that dynamic light scattering measurements may be carried out under such conditions. Varying the energy density of the ultrasonic field allows particles greater than a defined cut-off diameter to be removed from the measurement region. Theory shows that the minimum cut-off size may be as small as 100 nm. Results presented here demonstrate complete removal at a lower diameter threshold of approximately 2000 nm.     

Determination of Particle Size Distribution by the analysis of intensity-constrained multi-angle photon correlation spectroscopic data

Laser light scattering (LLS), especially dynamic laser light scattering (DLS), also known as photon correlation spectroscopy (PCS), is a well established method for particle size distribution analysis. It usually involves a Laplace inversion of the field autocorrelation function. However, the resolution is limited because of the ill-conditioned nature of this Laplace inversion. No unique solution exists when noise is present on the data. In contrast with this ill-conditioned nature, the angular dependence of scattered (static) intensities is precisely not ill-conditioned, which allows the resolution of the ill-conditioned inversion of DLS data to be improved. In order to characterize samples with more complicated size distributions, an intensityconstrained multi-angle PCS data analysis program has been developed, which is an alternative way of normalizing the field correlation function to that reported by Cummins and Staples [12]. In this program, the field autocorrelation function is normalized to the scattering intensity by using a predetermined coherent factor at each angle, which provides an additional constraint on the Laplace inversion of multi-angle PCS data analysis. The alternative analysis improves the resolution of PCS and provides a more reliable particle size distribution than single-angle data analysis. Both simulated and measured LLS data are used to illustrate its application, resolution and limitations.     

应用低相干动态光散射法测量悬浮液中的颗粒粒径分布

利用低相干动态光散射法测量不同浓度悬浮液中的颗粒粒径分布。由低相干光源和迈克尔逊干涉仪,结合传统的动态光散射技术组成低相干动态光散射装置,通过检测单次背散射光的能谱分布,利用CONTIN算法得到不同浓度悬浮液中颗粒的粒径分布。结果表明,对于1%～10%体积浓度范围内的单分散悬浮液羊品测量得到的颗粒粒径精确度在4%以内。     

Sizing Polydisperse Dispersions by Focused Beam Reflectance and Small Angle Static Light Scattering

In this work, two different methods for particle characterization, namely focused beam reflectance and small angle static light scattering, are quantitatively compared. The results are presented in the form of moment ratios of the particle size distribution, i.e., the number weighted diameter, D_1/0, and the volume weighted diameter, D_4/3, for a broad range of particle size distributions ranging from 20 to 400 μm. Various aqueous dispersions including narrow, broad, and bimodal particle size distributions of spherical shaped ceramic beads were used in the comparison. It was found that the moment ratios obtained by focused beam reflectance measurements and small angle static light scattering correlate well, in the case of spherical particles. Furthermore, it was found that the D_1/0 values obtained by focused beam reflectance measurements are more sensitive to the presence of a small fraction of fine particles in a bimodal distribution than those obtained by small angle static light scattering.     

Characterization of spherical core–shell particles by static light scattering. Estimation of the core- and particle-size distributions

A numerical method is proposed for the characterization of core–shell spherical particles from static light scattering (SLS) measurements. The method is able to estimate the core size distribution (CSD) and the particle size distribution (PSD), through the following two-step procedure: (i) the estimation of the bivariate core–particle size distribution (C–PSD), by solving a linear ill-conditioned inverse problem through a generalized Tikhonov regularization strategy, and (ii) the calculation of the CSD and the PSD from the estimated C–PSD. First, the method was evaluated on the basis of several simulated examples, with polystyrene–poly(methyl methacrylate) core–shell particles of different CSDs and PSDs. Then, two samples of hematite–Yttrium basic carbonate core–shell particles were successfully characterized. In all analyzed examples, acceptable estimates of the PSD and the average diameter of the CSD were obtained. Based on the single-scattering Mie theory, the proposed method is an effective tool for characterizing core–shell colloidal particles larger than their Rayleigh limits without requiring any a-priori assumption on the shapes of the size distributions. Under such conditions, the PSDs can always be adequately estimated, while acceptable CSD estimates are obtained when the core/shell particles exhibit either a high optical contrast, or a moderate optical contrast but with a high ‘average core diameter’/‘average particle diameter’ ratio.     

Characterisation of nanoparticle size and state prior to nanotoxicological studies

Before commencing any nanotoxicological study, it is imperative to know the state of the nanoparticles to be used and in particular their size and size distribution in the appropriate test media is particularly important. Particles satisfying standards can be commercially purchased; however, these invariably cannot be used directly and need to be dispersed into the relevant biological media. Often such changes in the environment or ionic strength, or a change in the particle concentration, results in some aggregation or a shift in the particle size distribution. Such unexpected aggregation, dissolution or plating out, if unaccounted for, can have a significant effect on the available nanoparticle dose and on interpretation of any results obtained thereafter. Here, we demonstrate the application of characterisation instrumentation that sizes nanoparticles based on their Brownian motion in suspension. Unlike classical light-scattering techniques, the nanoparticle tracking and analysis (NTA) technique allows nanoparticles to be sized in suspension on a particle-by-particle basis allowing higher resolution and therefore better understanding of aggregation than ensemble methods (such as dynamic light scattering (DLS) and differential centrifugation sedimentation (DCS)). Results will be presented from gold (standard) nanoparticles in biologically relevant media that emphasise the importance of characterisation of the nanoparticle dispersion. It will be shown how the NTA technique can be extended to multi-parameter analysis, allowing for characterization of particle size and light scattering intensity on an individual basis. This multi-parameter measurement capability allows sub-populations of nanoparticles with varying characteristics to be resolved in a complex mixture. Changes in one or more of such properties can be followed both in real time and in situ.     

颗粒系的可见消光光谱分析及最佳波长的选择

在光全散射法颗粒粒径测量中,被测颗粒系的消光光谱包含有颗粒粒径、折射率等信息。对常用的单峰及双峰R-R分布的可见消光光谱进行模拟,分析了可见消光光谱随粒径和相对折射率变化的规律。选取二阶微分可见消光光谱不连续点对应的波长作为测量波长,并将可见光边界波长同时作为测量波长,在非独立模式下,采用遗传优化算法反演粒径分布。仿真计算与实验验证结果表明,通过消光光谱分析,可以预先确定被测颗粒系的分布状况,缩小优化算法中反演参数的搜索范围。结合最佳波长选择方法,使测量的精度和可靠性明显提高。对测量光谱加入1%随机噪声时,单峰及多峰分布粒径反演均能得到满意的结果。     

Anomalous Coefficient of Ion Reflection from a Crystal under Surface-Channeling Conditions

A significant difference in behavior between the coefficients of deuterium-atom reflection upon scattering at crystal and amorphous tungsten is shown. The region where the reflection coefficient is close to 100% is determined by scattering at the first and second crystal layers and depends on the orientation. The effect of ion focusing on second-layer atoms and also various orientation effects are observed. It is shown that, at small grazing angles, the dependence of the reflection coefficient on the energy of transverse particle motion is universal. The dependences on the azimuthal exit angle ? exhibit the rainbow scattering effect caused by particle motion in the surface semichannel, while the dependences on the polar angle demonstrate the effect of angular distribution narrowing (ion focusing).     

Preparation and characterization of nano and micro particles of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) via emulsification/solvent evaporation and nanoprecipitation techniques

This paper describes the preparation and the characterization of micro and nanoparticles of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) via two different preparation techniques. The first technique is the emulsification/solvent evaporation while the second is the nanoprecipitation which is being reported for first time for the PHBV particles. The effect of various conditions of preparation on the size and the morphology of the produced particles was studied for both techniques. Field emission scanning electron microscopy, static light scattering and dynamic light scattering were used to analyse the size and the morphology of the particles. The particles produced using the emulsification/solvent evaporation were spherical porous micro and nanoparticles ranging from 300 up to 20 μm. The size, porosity and the particle size distribution were found to be controllable basically via choosing the surfactant and the polymer concentration when the emulsification technique was used. Choosing the appropriate anti-solvent and adjusting its polarity are crucial for getting spherical particles via nanoprecipitation. The micro and nanoparticles produced via both techniques are intended basically to be used for reinforcing biopolymeric matrices of PHBV and starches.