图像动态光散射法纳米颗粒粒度分布反演算法研究

针对基于整体相关的图像动态光散射法(IDLS)测量颗粒粒径分布(PSD)问题,研究了全局搜索(GS)算法反演颗粒粒径分布,对峰值为79nm、多分布指数(PDI)为10%的单峰颗粒系和峰值分别为79nm与352nm、多分布指数均为10%的双峰颗粒系进行了反演数值仿真,结果表明全局搜索算法能较好地反演出颗粒粒径分布情况。以此为基础,对峰值为79nm的单峰分布颗粒系,峰值为79nm和352nm、79nm和482nm的两组双峰分布颗粒系进行了实验测量及算法对比研究,结果表明在单峰分布颗粒系下,相对于累积量法,全局搜索算法反演效果较好;在双峰分布颗粒系下,全局搜索算法与双指数法反演结果基本一致。由此可知,对于图像动态光散射颗粒粒径分布测量方法,全局搜索算法能够有效地反演出单峰分布和双峰分布颗粒系的颗粒粒径分布,是反演多分散颗粒系的一种有效方法。     

多频声衰减法测量低密度差异液固两相流粒径分布

针对低密度差异液固两相流的分散相粒径分布测量问题,提出多频超声衰减测量方法。以ECAH (Epstein Carhart Allegra Hawley theory)理论模型为基础,分析了不同物性参数对多频超声衰减的影响,建立了分散相粒径分布与多频超声衰减之间的理论关系,用于计算被测流体中超声衰减的理论预测值。通过构造实测多频衰减与待求粒径分布间的目标函数,将粒径分布的反演表示为优化问题,利用高斯量子粒子群算法对不同粒径颗粒浓度参数寻优,实现粒径分布的反演。以微米级聚苯乙烯颗粒与水制备的悬浮液作为研究对象,在搅拌条件下进行动态实验。实验结果表明,利用4~11 MHz的多频超声衰减测得的粒径分布,与Mastersizer 2000激光粒度分析仪的测量结果基本一致,平均粒径误差为5.60%。     

夫琅和费衍射颗粒粒度测量中的改进Chin-Shifrin反演算法

在基于线阵CCD的夫琅和费衍射颗粒粒度测量中,采用Chin-Shifrin积分变换反演算法使得反演的粒度分布出现假峰现象.为解决此问题,提出在该Chin-Shifrin积分变换反演算法中引入矩形窗函数,并在分析颗粒粒径与衍射光强导数最小值之间关系的基础上,确定矩形窗函数中心点位置及左右边界,利用该矩形窗函数对粒度分布进行截断处理,消除虚假峰,提高反演颗粒粒度分布的准确性.分别对两种标准颗粒进行了测量,并对不同算法的反演结果进行了对比.实验结果表明:引入矩形窗函数的改进Chin-Shifrin算法,能够有效排除粒度分布中的多假峰;粒度分布测量相对误差小于3%,重复性小于4%.     

多分散Au-Ag合金纳米球的光谱消光法反演

贵金属纳米颗粒具有局域表面等离子体共振特性而引起了广泛的关注,其中Au-Ag合金纳米颗粒具有良好的结构稳定性、光热性能以及潜在的抗癌功效而得到普遍研究。在众多应用中的特性与其粒径和浓度密切相关,然而目前常用的电子显微镜观察法和动态光散射法不能同时获得粒径和浓度信息,因此采取有效手段测量颗粒粒径和浓度信息至关重要。基于光谱消光法,利用非负的Tikhonov正则化方法解决反演问题,并根据Mie理论计算消光矩阵。针对噪声问题,采取两种情况研究多分散Au-Ag合金纳米球粒径分布与浓度的反演问题。未添加噪声情况下,颗粒系Ⅰ的反演相对误差小于颗粒系Ⅱ,在波长范围300～500 nm之间的反演相对误差最小,对应平均粒径、粒径标准差和颗粒数浓度的反演相对误差分别为0%,-0.03%和0%。添加随机噪声情况下,将0.5%和1.0%的随机噪声添加进颗粒系Ⅰ中的消光谱,经过数据比较发现在波长范围200～600 nm之间的反演相对误差最小。当添加0.5%的随机噪声时,粒径分布、粒径标准差和颗粒数浓度的变化范围分别为79.76～80.15 nm, 5.60～6.61 nm和0.995 8×1010～1.005 9×1010个·cm-3;当添加1.0%的随机噪声时,粒径分布、粒径标准差和颗粒数浓度的变化范围分别为78.87～80.27 nm, 5.36～9.00 nm和0.992 4×1010～1.027 7×1010个·cm-3。反演结果随着随机噪声的增大,变化范围也明显增大即反演相对误差增大,并且每次添加相同随机噪声后的反演结果不同。为了减少随机噪声导致的不稳定性,对100次反演结果进行平均得到平均粒径、粒径标准差和颗粒数浓度。当随机噪声从0.5%增大至1.0%时,其反演结果的相对误差均增大,但是反演得到的粒径分布、粒径标准差和颗粒数浓度相对误差均小于6%,这说明通过反演算法得到的反演结果具有较好的稳定性。研究表明,光谱消光法为反演多分散Au-Ag合金纳米球粒径分布与浓度提供了一种简单、快速的表征手段,也对研究非球形纳米颗粒有启示作用。     

非独立模式算法下粒径分布反演及分类的研究

在光全散射法颗粒粒径测量中,提出一种非独立模式算法下粒径分布反演及分类的方法。对被测颗粒系分别按照不同的粒径分布函数同时进行反演,并依据反演误差大小判断被测颗粒系符合哪种分布函数。仿真实验结果表明,在非独立模式下,完全可以利用已知的不同分布函数的反演误差作为分类依据,从而更准确地确定被测颗粒系的粒径分布。采用的遗传反演算法能够在3个可见光波长下得到较准确的粒径分布,反演结果稳定可靠,最大限度地减少了多个波长的使用,从而对光源有更大的选择余地。对透射消光测量结果加入5%随机噪声时,单峰分布颗粒系的反演误差小于5%,多峰分布颗粒系的反演误差小于10%。整个算法运行时间小于2 s。该方法具有原理简单,计算速度快等优点,能够满足颗粒粒径在线测量的要求。     

基于模式搜索的光谱消光粒径分布反演算法的研究

发展快速有效的反演算法用于粒径分布的重建是颗粒测量领域重要的研究课题之一。在光谱消光法粒径测量中,提出将模式搜索算法用于独立模式下粒径分布的重建,同时引入Tikhonov平滑泛函构建算法的目标函数,为保证搜索过程的快速性和准确性,设计了关于初始点的优选策略。利用该算法测量国家标准颗粒体积平均直径的相对误差为3.14%,不超过国家标准物质局给出的±8%的范围,且粒径分布宽度合理,没有明显展宽和伪峰现象。与Phillips-Twomey方法和遗传算法的对比结果表明,在综合考虑反演精度和反演时间条件下,该算法具有明显优势,更适合于快速准确的现场测量,具有较好的应用前景。     

韦伯分布布谷鸟搜索算法颗粒粒径分布反演

韦伯分布在非线性寻优问题中具有较好的寻优精度和全局搜索能力,为此提出一种基于韦伯分布的布谷鸟搜索（WCS）算法来解决颗粒粒径分布反演的问题。使用WCS算法对服从Johnson’s S_B分布、Rosin-Rammler分布和正态分布的单峰颗粒系和双峰颗粒系进行颗粒粒径分布的反演,并分别与其他传统算法的处理结果进行比较。结果表明,WCS算法的整体效果优于人工鱼群算法和人工蜂群算法,且改进后的4种重尾分布CS算法的标准差比原CS算法提升2～3个数量级。目标函数散射光能加入噪声后,WCS算法比其他三种重尾分布的相对均方根误差值至少可降低1/2。使用小角前向散射测量系统对单峰颗粒系和双峰混合颗粒系进行实验研究,发现WCS算法的相对均方根误差比原CS算法降低约为40%。     

激光自混合干涉法亚微米及纳米颗粒测量中的反问题

基于Kaczmarz投影算法对反问题进行了详细的研究.选取颗粒线分布函数作为反演对象,改进了Kaczrnarz投影算法,使投影过程发生在较大夹角的超平面之间.数值模拟了含5%和10%的测量误差时宽单峰、窄单峰、双峰和三峰四种粒径分布的反演,结果显示改进投影算法得出的粒径分布与输入的粒径分布更好得吻合.实验测量了标称为60 mn和180 nm两种单分散颗粒,结果表明改进投影算法得出的粒径分别为54.95 nm和190.55 nm,而原先投影算法得出的粒径为83.18 nm和288.40nm,进一步显示改进投影算法提高了测量结果的准确性.     

基于超声衰减谱的纳米颗粒粒度分布测量研究

利用变声程方式测量纳米颗粒悬浮液的超声衰减谱,以McClements模型和BLBL模型为理论基础,采用最优正则化(ORT)算法,反演得到纳米颗粒的粒度分布。运用该方法,对体积浓度1%的纳米二氧化钛-水悬浊液进行测量,与透射电镜(TEM)图像以及离心沉降纳米粒度分析仪检测结果对比,测量结果吻合较好,表明了利用超声衰减谱方法测量纳米颗粒粒度分布的可行性与可靠性。      

基于彩虹现象的光学测粒技术研究

对基于彩虹现象的光学颗粒测量进行研究,提出了一种新的参数反演模型和算法,可同时测量颗粒的粒径和折射率.新算法基于经验模态分解的去噪技术,并采用一种特征点提取技术和基于Debye理论的反演最优点搜索算法,能较精确的迅速找到反演最优点.数值模拟结果表明,当信噪比降至5 dB时,直径反演最大误差小于10%,折射率反演最大误差小于0.1%.对不同温度下自由下落的水滴进行实验研究,水滴由波长532 nm功率14 mW的连续激光源照射, 产生的彩虹光线经大口径透镜收集,被位于透镜焦平面的CCD相机接收.实验结果同样表明此测量方法具有较好的精度和可靠性.     

On-Line Particle Size Analysis Using Ultrasonic Velocity Spectrometry

A new method is described for the determination of particle size distribution of slurries based on ultrasonic velocity spectrometry combined with gamma-ray transmission. This method shares the advantages of ultrasonic attenuation spectroscopy of being capable of analyzing highly concentrated samples without dilution. However the ultrasonic velocity method is better suited to fine particles of diameter from about 0.1 to 30 μm, a greater volume of slurry is analysed and therefore sampling errors are reduced, and precise theoretical models are readily available to permit the accurate determination of size distribution by inversion of ultrasonic velocity measurements. The method can also be used to accurately determine particle size cut points by linear correlation. Using either inversion or correlation methods, the accuracy of particle size information from ultrasonic velocity spectroscopy is significantly enhanced by the independent measurement of solids loading by gamma-ray transmission. In addition, larger sizes can be measured by combining the ultrasonic velocity method with ultrasonic attenuation measurements. The method has been tested in the laboratory on a wide variety of mineral and paint slurries. The method determined the size distribution of single component silica and alumina samples in water in agreement with laser diffraction measurements and the method successfully distinguished well and poorly dispersed TiO₂ suspensions. For composite samples the method discriminated separate TiO₂ and CaCO₃, components and determined their proportions to within 0.25% volume. In addition the method, in combination with ultrasonic attenuation measurements, determined the size fractions of iron ore slurries below 10 and 30 μm to within 1.3% and 1.0% relative respectively, when compared with laser diffraction measurement of particle size. The CSIRO is presently designing an industrial gauge which will be manufactured and installed in an industrial slurry stream in 1997.     

Ultrasonic Spectrometry for Particle Size Analysis in Dense Submicron Suspensions

Ultrasonic spectrometry was applied to the particle size analysis of disperse systems. The investigations were made for acoustic conditions called the long-wavelength regime (LWR). In the LWR the acoustic behaviour is governed by dissipative effects rather than by scattering. Two principal theoretical approaches to ultrasonic spectrometry — scattering theory and coupled phase models — are introduced. A model based on a newly developed coupled phase model and the scattering theory (ECAH theory) is implemented in the ultrasonic spectrometer Acousto Phor. Experiments were carried out for several suspensions with a high density contrast. It could be demonstrated that the model successfully describes acoustic attenuation and that the inversion algorithm finds particle size distributions comparable to those given by other measurement techniques. With regard to the particle size, a lower and an upper limit for the applicability were determined, which include three decades. As a further result, the model was validated at concentrations up to 10 vol.%. The model is considered to be open to development to cover even higher concentrations.     

Information Content of Acoustic Attenuation Spectra

In recent years ultrasonic attenuation spectroscopy has gained much attention as a method for the characterisation of concentrated dispersions. Several publications have shown, that this method allows the accurate determination of particle size. In particular for submicron dispersions there is, however, some uncertainty to which degree the details of a size distribution can be resolved by acoustic attenuation measurements. Ideally the inversion of an attenuation spectrum into a size distribution would yield as much distribution parameters as sound frequencies. In practice, however, the measurement errors affect the inversion very strongly and may result in multiple solutions for the size distribution. The maximum number of distribution parameters, for which a unique solution exists, can be therefore regarded as the information content. For a given ultrasonic spectrometer and material system it is possible to quantify the information content. Such an information analysis has been conducted with selected material systems in the submicron range. The investigation shows that the information content of acoustic attenuation spectra with regard to particle size analysis in the submicron range is relatively low. On the other hand, the results imply that the number of frequencies can be reduced significantly without loss of information content or stability of inversion algorithms.     

Ultrasonic Measurement of Sub-Micron Particles

Based on technology described in a Du Pont patent for an offline system, we have developed a prototype in-line ultrasonic cell for measuring particle size distribution. We have used this cell to verify the Allegra-Hawley model of ultrasonic attenuation in dilute (< 5 % vol) slurries of sub-micron ceramic particles, and we are developing a model that can cope with the multiple scattering effects occuring at higher concentrations. In this paper we present the results of attenuation measurements for ultrasound (2–50 MHz) in slurries with concentrations ranging from 0.5 010 to 38 010 (vol). The attenuation is proportional to slurry concentration up to 5 010 (vol) and is predicted by single scattering models. Above approximately 100% concentration, the attenuation is actually lower than expected. For the dilute slurries we find excellent agreement between our measurements and the Allegra-Hawley calculations, and the effects of the particle size distribution are evident in the ultrasonic attenuation spectrum. These ultrasonic data can be inverted to determine the particle size and concentration in aqueous slurries of sub-micron particles.     

超声衰减和速度谱测量亚微米乳液的粒径

研究了超声衰减谱法和相速度测量高浓度多分散脂肪两相乳浊液的粒径分布问题.在理论分析基础上,实验测量了多个浓度(2%～20%)脂肪乳试样在2～13 MHz频带下超声衰减和相速度谱,结合反演算法由实验数据计算出乳浊液颗粒的粒径分布,并讨论了相速度法的意义和特点.将原始浓度(20%)下测得粒径分布与消光法在稀释条件下相同试样测量结果作对比,二者比较吻合,表明超声谱法可在无稀释的高浓度条件下作乳浊液粒径分布的表征.     

A study on measuring distribution of nanoparticle size based on ultrasonic attenuation spectrum

Through varying the ultrasonic path length,the ultrasonic attenuation spectrum of the nanometer particle suspensions is measured.Based on the McClements and BLBL model, the Optimum Regularization Technique is employed to inverse the distribution of particle size for nanometer particles.Experiments are carried out to measure the distribution of particle size of aqueous nanometer titanium dioxide suspension with volume fraction of 1%.The ultrasonic measurement results show good consistence with those from TEM(Transmission Electron Microscope) and centrifugal sedimentation particle size analyzers,which indicate that measuring distribution of the particle size of nanometer particles with the ultrasonic attenuation spectrum is feasible and reliable.     

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。