Characterization of suspensions of particles in water by an ultrasonic resonant cell

This paper presents a resonant technique to accurately measure phase-velocity and attenuation of longitudinal acoustic waves in suspensions of solid particles in water. The technique is based on exciting thickness resonances of a layer of fluid and analyzing its spectrum. To this end, a resonant cell to contain the fluid is described and used. Two different type of water suspensions are studied: titanium dioxide and alumina particles; particle volume fraction is in the range 0–0.18. Simultaneous determination of particle size distribution in the suspension by an optical method are also carried out. Finally, the experimental results are compared with theoretical predictions obtained from three different approaches.     

Velocity fluctuations in fluidized suspensions probed by ultrasonic correlation spectroscopy

Velocity fluctuations in a fluidized suspension of particles are investigated using two new ultrasonic correlation spectroscopies: diffusing acoustic wave spectroscopy and dynamic sound scattering. These techniques probe both the local strain rate and rms velocity of the particles, providing important information about the spatial extent of velocity correlations. Our results demonstrate the power of these techniques to probe particle dynamics of fluidized suspensions, and suggest that the velocity correlations are essentially independent of Reynolds numbers for Re(p)<1.     

等离子体光谱/质谱中悬浮液进样研究进展

等离子体光谱/质谱法是无机元素分析主要的分析方法之一,但其通常要求以溶液形式进样。文章在介绍目前几种固体试样直接进样方法的基础上,着重对悬浮液进样等离子体光谱/质谱研究进展进行综述。叙述悬浮液的制备方法及表征,包括球磨法、混合研磨、振动球磨、超声研磨等降低颗粒的方法。通过分散剂、pH调节等方法分散和稳定悬浮液,并就其关系进行阐述。叙述粒度大小分布测量的几种方法：沉降法、光学显微镜法、光透沉降式粒度仪法、激光散射法、扫描或透射电镜法等。讨论悬浮液浓度影响以及校准方法技术：简单水溶液标准校准法、内标法、经验校正系数法、标准加入法、本征内标法、标准悬浮液法。综述了悬浮液进样的有关基础研究和近年悬浮液进样等离子体光谱/质谱分析应用。     

Lanthanide Luminescence as a Probe of Nanocrystalline Materials

The sharp lines in the optical spectra of lanthanide ions in solids are sensitive to the local environment surrounding the ion and, therefore, provide a local probe to study new materials. This paper reports the laser spectroscopic characterization of a series of Eu₂O₃ nanocrystals, which serve as a model compound for understanding the spectroscopy of lanthanides in nanocrystalline materials. The optical spectra of Eu₂O₃ particles with diameters of approximately 18 to 4 nm show an increase in inhomogeneous broadening and a transition to a very disordered phase as the particle size decreases. The ⁵D₀ fluorescence transients of the nanocrystals are shorter than in bulk material show no clear trend as a function of particle size but do become single exponential for 6- and 4-nm particles.     

Particle Size of Pneumatically Conveyed Powders Measured Using Impact Duration

CSIRO Minerals has developed a technique for measuring particle size in pneumatically conveyed powders [1] by measurement of the acoustic waves produced by particle impacts upon a specially designed transducer. Previous work has focused on using the peak acoustic wave amplitude to determine particle size. This produces a spectrum that is hard to determine the particle size from, as the peak amplitude is a non‐linear function of particle diameter, and is strongly affected by angle of incidence and velocity of the impacting particle. In this paper impact duration measurements are used to overcome these difficulties while retaining the advantages of being able to measure in high solids loadings of up to at least 0.5 kg/m³ of powder. In laboratory tests the impact size monitor's (ISM) results have been correlated with optical diffraction measurements of the mean (by number) powder size with a correlation coefficient of 0.985 and a relative error of 5.5 %. The ISM operated successfully in the laboratory at a loading of 0.5 kg/m³ of powder and measured particles down to 50 microns in size.     

Particle levitation and laboratory scattering

Measurements of light scattering from aerosol particles can provide a non-intrusive in situ method for characterising particle size distributions, composition, refractive index, phase and morphology. When coupled with techniques for isolating single particles, considerable information on the evolution of the properties of a single particle can be gained during changes in environmental conditions or chemical processing. Electrostatic, acoustic and optical techniques have been developed over many decades for capturing and levitating single particles. In this review, we will focus on studies of particles in the Mie size regime and consider the complimentarity of electrostatic and optical techniques for levitating particles and elastic and inelastic light scattering methods for characterising particles. In particular, we will review the specific advantages of establishing a single-beam gradient force optical trap (optical tweezers) for manipulating single particles or arrays of particles. Recent developments in characterising the nature of the optical trap, in applying elastic and inelastic light scattering measurements for characterising trapped particles, and in manipulating particles will be considered.     

Characterization of Nano‐Particles Using Laser‐Induced Incandescence

Laser‐induced incandescence (LII) is introduced as a valuable tool for the characterization of nanoparticles. This optical measurement technique is based on the heating of the particles by a short laser pulse and the subsequent detection of the thermal radiation. It has been applied successfully for the investigation of soot in different fields of application, which is described here in the form of an overview with a focus on work done at the LTT‐Erlangen during the last 10 years. In laboratory flames the soot primary particle size, volume concentration, and relative aggregate size have been determined in combination with the number density of primary particles. Furthermore, the primary particle sizes of carbon blacks have been measured in situ and online under laboratory conditions and also in production reactors. Measurements with different types of commercially available carbon black powders, which were dispersed in a measurement chamber yielded a good correlation between LII results and the specified product properties. Particle diameters determined by LII in a furnace black reactor correlate very well with the CTAB‐absorption number, which is a measure for the specific surface area. It turned out that the LII method is not affected by variations of the aggregate structure of the investigated carbon blacks. The LII signal also contains information on the primary particle size distribution, which can be reconstructed by the evaluation of the signal decay time at, at least, two different time intervals. Additionally, soot mass concentrations have been determined inside diesel engines and online measurements were performed in the exhaust gas of such engines for various engine conditions simultaneously providing information about primary particle size, soot volume, and number concentration. The LII results exhibit good correlation with traditional measurement techniques, e.g., filter smoke number measurements. In addition to the soot measurements, primarily tests with other nanoparticles like TiO₂ or metal particles are encouraging regarding the applicability of the technique for the characterization of such different types of nanoparticles.     

Characterization of Pyrogenic Powders with Conventional Particle Sizing Technique: I. Prediction of Measured Size Distributions

Pyrogenic powders consist of fractal like aggregates with nanosized primary particles. The formation of such aggregates, their hydrodynamic behavior and their optical properties are in principle well understood. Even so, there is only little experience in interpreting results from particle sizing of such materials. Dramatic differences in size distribution obtained from different measurement techniques give frequently rise to confusion on the “true” aggregate size. However, such differences can be attributed to the different particle properties used for size measurement and to the different types of quantities, by which the frequency of the individual size fractions are weighted. For two conventional sizing techniques, Dynamic Light Scattering and Optical Centrifugation Analysis, the influence of the structural properties on the relevant optical and hydrodynamic aggregate properties is discussed on the basis of virtual aggregates as well as of empirical data for pyrogenic powders. Finally measurable size distributions are predicted in a case study.     

In situ characterization of nanoparticles during growth by means of white light scattering

A simple method of characterization of suspensions of spherical nanoparticles with monotonically variable size is proposed. It allows for the in situ measurement of the particle size as well as spectral dependence of their refractive indices. The method requires three optical channels: one for the illumination of a suspension by white light and two for the measurements of the spectra of scattered light. Parameters of the particles are determined by fitting the measured temporal spectral surfaces by the calculated Mie scattering functions. The method is applied to the particles being grown in a low-pressure reactive plasma of a discharge in an acetylene-argon mixture.     

Polydisperse particle size characterization by ultrasonic attenuation spectroscopy in the micrometer range

The theoretical advantages of ultrasonic attenuation spectroscopy for particle size are currently not fully utilized. Especially in the region of larger particles, there is a lack of experimental confirmation of applicable models which may be used to infer particle sizes from measured attenuation spectra. With the present work, an attempt is made to supply experimental data, obtained with a commercially available ultrasonic attenuation spectrometer, and model calculations, which are based on the resonant scattering theory. It is shown that measured attenuation results for various combinations of disperse and continuous phase for both polydisperse emulsions and suspensions are reproducible by calculation. The approach is further examined for suspensions of porous particles. Here, the resonant scattering approach is combined with the Biot model for poroelasticity to obtain attenuation results with several fractions of titania aggregates, differing in particle size and pore diameter. The results indicate that the theory of resonant scattering is a valid approach if applied to particle size characterization in the large particle limit.     

Determination of Particle Size Distribution and Electrokinetic Properties with the AcoustoSizer in Comparison with Other Methods

The characterization of suspensions in process concentration is an important task for the optimization of handling and product properties. Only very few instruments are available. The AcoustoSizer (ACS) (Colloidal Dynamics PTY Ltd.) uses the so-called electrokinetic sonic amplitude (ESA) for particle size and zeta potential determination. In this work, the results obtained at moderate concentrations were compared with results of other instruments mostly working with dilute suspensions. For the electrokinetic investigations three methods (beside the ACS) were used: electroacoustics (ESA8000, Matec Applied Sciences), microelectrophoresis (Zetamaster, Malvern Instruments) and streaming current measurements (Particle Charge Detector PCD 03-pH, Miitek). For particle size determination different measuring techniques were applied: laser diffraction spectroscopy (Mastersizer S, Malvern Instruments), dynamic light scattering (Ultra Fine Particle Analyser, Leeds and Northrup), sedimentation analysis (Sedigraph 5000 D, Micromeritics) and scanning electron microscopy. Mainly three powders were used in the investigations: Monospher M1200 silica (Merck), Selectipur titania (Merck) and Aluminiumoxid C alumina (Degussa). The agreement between the different methods for both particle size and zeta potential measurements was excellent. Especially for the electrokinetic investigations, careful sample preparation is needed. The procedure must not change the equilibria determining the physical and chemical state of the suspension.     

Determination of optical constants of latex in concentrated suspensions

The possibility of taking into account concentration effects in the determination of optical constants of latex in the visible and near IR regions of the spectrum is demonstrated, and the limits of applicability of the methods proposed for this purpose are determined. The limiting concentration of particles in suspensions for which these effects should be taken into account depend on the particle size. Using latex as an example, ways of increasing the accuracy of reconstruction of optical constants of weakly absorbing particles of micron and submicron size are shown. Similar concentration effects can take place in the study of blood substituents, proteins, and other weakly absorbing particles in weakly absorbing media.     

Measurement of the index of refraction of single microparticles

The refractive index of single microparticles is derived from precise measurement and rigorous modeling of the stiffness of a laser trap. We demonstrate the method for particles of four different materials with diameters from 1.6 to 5.2 microm and achieve an accuracy of better than 1%. The method greatly contributes as a new characterization technique because it works best under conditions (small particle size, polydispersion) where other methods, such as absorption spectroscopy, start to fail. Particles need not be transferred to a particular fluid, which prevents particle degradation or alteration common in index matching techniques. Our results also show that advanced modeling of laser traps accurately reproduces experimental reality.     

Characterizing the dynamic behavior of nano-TiO<Subscript>2</Subscript> agglomerates in suspensions by photocorrelation spectroscopy

Metal oxide nanoparticles are small but easily form agglomerates in suspension, depending on the strength of particle–particle and particle–media interactions. To understand the agglomeration behavior of nanoparticles in media and relate to it to product performance testing, measurement methods are desired to characterize highly scattering metal oxide nanoparticle suspensions without dilution. In this article, we describe the advantages of using photocorrelation spectroscopy (PCS) in a backscattering detection configuration to carry out a realistic agglomerate size measurement in multiple scattering media found in most metal oxide nanoparticle suspensions. The dynamic behavior of nano-titanium dioxide (TiO₂) particles in buffer solutions of different chemical composition and pH values was investigated as a sample system using PCS. The resulting autocorrelation functions (AFs) at different time intervals, particle concentrations, and pH values were measured at several detection angles. The AF exhibits a multi-mode relaxation time feature and the calculated hydrodynamic diameters strongly depended on media composition and detection angle. This result indicates that the size and dispersion of nano-TiO₂ agglomerates are significantly affected by solution media. A measurement protocol for determining size and dispersion of metal oxide particles in media is proposed and related to a performance test found in industry.     

Determination of aerosol extinction coefficient and mass extinction efficiency by DOAS with a flashlight source

With the method of differential optical absorption spectroscopy （DOAS）, average concentrations of aerosol particles along light path were measured with a flashlight source in Chiba area during the period of one month. The optical thickness at 550 nm is compared with the concentration of ground-measured suspended particulate matter （SPM）. Good correlations are found between the DOAS and SPM data, leading to the determination of the aerosol mass extinction efficiency （MEE） to be possible in the lower troposphere. The average MEE value is about 7.6m^2.g^-1 , and the parameter exhibits a good correlation with the particle size as determined from the wavelength dependence of the DOAS signal intensity.     

Improved pulsed broadband ultrasonic spectroscopy for analysis of liquid-particle flow

The paper contains an investigation of broadband pulsed ultrasonic spectroscopy techniques, intended for testing of suspensions, such as a liquid-particle flow containing small diameter particles. Influence of traditional and novel broadband pulse shapes on quality of frequency spectra is analysed, as well as pulse design aspects leading to an optimal shape of an ultrasonic excitation wave. Effects that may influence signal quality and method reliability in a given setup, in particular resonances and noise are discussed. Solutions for signal acquisition and averaging techniques are presented, as well as results of testing of instrumentation limits and overall performance. Results of acoustic spectroscopy measurement of a concentrated liquid-particle flow are provided. A number of experimental and numerical examples, together with comprehensive explanations, show a potential for ultrasonic attenuation spectroscopy to be a successful methodology for an on-line measurement of fluid-particle suspensions and composite non-homogeneous materials in general.     

Monitoring the liquid phase concentration by Raman spectroscopy in a polymorphic system

In this work, Raman spectroscopy was successfully used for the quantitative determination of the liquid phase concentration in an aqueous polymorphic system of D‐mannitol. An extensive study has initially been performed to identify the influence of the solid state, e.g. particle size, particle amount, and different polymorphs, on the intensity of the characteristic Raman solute signal. It was found that the existence of solid phase can decrease Raman intensity, and this influence is more significant when the suspension density is higher, e.g. with smaller size and larger amount of particles. Based on this information, a large number of samples were examined by Raman spectroscopy in the form of clear solutions and suspensions. The spectral preprocessing and partial least squares (PLS) regression were then used to relate the solute concentrations to these spectral data, independent of solid state. Several PLS calibration models were developed with different treatments to the spectral data, and the optimized strategy was finally demonstrated. Particularly, a reference peak at 578 cm⁻¹ related to the sapphire in the Raman probe window was innovatively applied to reduce the influences from the equipment and other external variations, with which the full‐spectrum PLS model was seen to give more stable results rather than partial spectral regions. The optimized model was subsequently applied to predict the liquid phase concentration in a multiphase multicomponent dynamic process, the solvent mediated polymorphic transformation (SMPT) of mannitol, and it was shown that the offline measurements and the predicted values were mainly in agreement with one another. Copyright © 2015 John Wiley & Sons, Ltd.     

Stimulated Low-Frequency Raman Scattering in LaF<Subscript>3</Subscript> Suspensions

We observe stimulated low-frequency Raman scattering (SLFRS) caused by laser pulse interaction with acoustic vibrations of nanoparticles in water suspensions of LaF₃ nanoparticles. We show that frequency shifts of the scattering correspond to the eigenfrequencies of nanoparticles vibrations. LaF₃ nanoparticles were synthesized in the presence of glycine by a double jet precipitation technique at various initial concentrations of reagents. We investigate the morphologies and particle sizes as well as size distributions of the particles prepared using transmission electron microscopy (TEM) and dynamical light scattering (DLS). In view of the absorption spectroscopy, we show that the reaction system components and products have no absorption in the visible region, including λ = 694.3 nm. From the luminescence spectroscopy, we find also that they do not emit at λ = 694.3 nm excitation.     

Results of potential exposure assessments during the maintenance and cleanout of deposition equipment

This study is a compilation of results obtained during the cleanout of deposition equipment such as chemical vapor deposition or physical vapor deposition The measurement campaigns aimed to evaluate the potential exposure to nanoaerosols in the occupational environment and were conducted in the workspace. The characterization of aerosols includes measurements of the concentration using condensation particle counters and measurements of the size distribution using fast mobility particle sizer, scanning mobility particle sizer, and electrical low pressure impactor (ELPI). Particles were sampled using collection membranes placed on the ELPIs stages. The samples were analyzed with an SEM?CEDS to provide information including size, shape, agglomeration state, and the chemical composition of the particles. The majority of the time, no emission of nanoparticles (NPs) was measured during the use of the molecular deposition equipment or when opening the chambers, mainly due to the enclosed processes. On the other hand, the maintenance of the equipment, and especially the cleanout step, could induce high concentrations of NPs in the workplace following certain processes. Values of around 1 million particles/cm³ were detected with a size distribution including a high concentration of particles around 10?nm.     

Influence of electron beam irradiation on structural and optical properties of α-Ag2WO4 nanoparticles

The influence of 8 MeV electron beam irradiation on the structural and optical properties of silver tungstate (α-Ag₂WO₄) nanoparticles synthesized by chemical precipitation method was investigated. The dose dependent effect of electron irradiation was investigated by various characterization techniques such as, X-ray diffraction, scanning electron microscopy, UV–vis absorption spectroscopy, photoluminescence and Raman spectroscopy. Systematic studies confirm that electron beam irradiation induces non-stoichiometry, defects and particle size variation on α-Ag₂WO₄, which in turn results changes in optical band gap, photoluminescence spectra and Raman bands.