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.     

Effects of Al(OH)O nanoparticle agglomerate size in epoxy resin on tension,bending, and fracture properties

Several epoxy Al(OH)O (boehmite) dispersions in an epoxy resin are produced in a kneader to study the mechanistic correlation between the nanoparticle size and mechanical properties of the prepared nanocomposites. The agglomerate size is set by a targeted variation in solid content and temperature during dispersion, resulting in a different level of stress intensity and thus a different final agglomerate size during the process. The suspension viscosity was used for the estimation of stress energy in laminar shear flow. Agglomerate size measurements are executed via dynamic light scattering to ensure the quality of the produced dispersions. Furthermore, various nanocomposite samples are prepared for three-point bending, tension, and fracture toughness tests. The screening of the size effect is executed with at least seven samples per agglomerate size and test method. The variation of solid content is found to be a reliable method to adjust the agglomerate size between 138–354 nm during dispersion. The size effect on the Young’s modulus and the critical stress intensity is only marginal. Nevertheless, there is a statistically relevant trend showing a linear increase with a decrease in agglomerate size. In contrast, the size effect is more dominant to the sample’s strain and stress at failure. Unlike microscaled agglomerates or particles, which lead to embrittlement of the composite material, nanoscaled agglomerates or particles cause the composite elongation to be nearly of the same level as the base material. The observed effect is valid for agglomerate sizes between 138–354 nm and a particle mass fraction of 10 wt%.     

Dynamic forces on agglomerated particles caused by high-intensity ultrasound

In this paper the acoustic forces on particles and agglomerates caused by high-intensity ultrasound in gaseous atmosphere are derived by means of computational fluid dynamics (CFD). Sound induced forces cause an oscillating stress scenario where the primary particles of an agglomerate are alternatingly pressed together and torn apart with the frequency of the applied wave. A comparison of the calculated acoustic forces with respect to the inter particle adhesion forces from Van-der-Waals and liquid bridge interactions reveals that the separation forces may reach the same order of magnitude for 80 μm sized SiO₂-particles. Hence, with finite probability acoustically agitated gases may de-agglomerate/disperse solid agglomerate structures. This effect is confirmed by dispersion experiments in an acoustic particle levitation setup.     

Study of the mobility,surface area,and sintering behavior of agglomerates in the transition regime by tandem differential mobility analysis

The surface area of nanosized agglomerates is of great importance as the reactivity and health effects of such particles are highly dependent on surface area. Changes in surface area through sintering during nanoparticle synthesis processes are also of interest for precision control of synthesised particles. Unfortunately, information on particle surface area and surface area dynamics is not readily obtainable through traditional particle mobility sizing techniques. In this study, we have experimentally determined the mobility diameter of transition regime agglomerates with 3, 4, and 5 primary particles. Agglomerates were produced by spray drying well-characterised polystyrene latex particles with diameters of 55, 67, 76, and 99 nm. Tandem differential mobility analysis was used to determine agglomerate mobility diameter by selecting monodisperse agglomerates with the same number of primary particles in the first DMA, and subsequently completely sintering the agglomerates in a furnace aerosol reactor. The size distribution of the completely sintered particles was measured by an SMPS system, which allowed for the determination of the number of primary particles in the agglomerates. A simple power law regression was used to express mobility diameter as a function of primary particle size and the number of primary particles, and had an excellent correlation (R² = 0.9971) with the experimental data. A scaling exponent was determined from the experimental data to relate measured mobility diameter to surface area for agglomerates. Using this relationship, the sintering characteristics of agglomerates were also examined for varying furnace temperatures and residence times. The sintering data agreed well with the geometric sintering model (GSM) model proposed by Cho & Biswas (2006a) as well as with the model proposed Koch & Friedlander (1990) for sintering by viscous flow.     

Identification of the Dispersion Behavior of Surface Treated Nanoscale Powders

The stability of highly acidic metal oxide surface treatments on rutile titanium dioxide nanopowders (40 nm nominal particle size) is examined. Dispersions are characterized in terms of their sedimentation behavior and light scattering pattern. Using elliptically polarized light scattering (EPLS), agglomerates are identified as fractal structures and size analysis is performed according to the measured fractal dimension. The effect of ultrasonication on agglomerate size and structure (compactness) is quantified for tungsten oxide and molybdenum oxide surface treatments, as well as untreated titanium oxide. Surface treatments are shown to increase dispersion stability, as witnessed by the decreased size of large agglomerates and sedimentation behavior. The EPLS fractal studies, combined with ultrasonication analysis, reveals information of agglomerate shapes, primary particle bonds and structures, and agglomerate growth mechanisms.     

Influence of the Particle Morphology on the Activity of Nanometer Platinum Aerosol Catalysts

For nanoparticle agglomerates, the catalytic activity may depend strongly on their structure. The influence of different parameters such as agglomerate structure, primary particle temperature history and surface preconditioning on the catalytic activity of nanoparticles was investigated. The fraction of agglomerate surface contributing to the reaction depends on the agglomerate structure and on the velocity of the reaction under investigation. For extremely fast reactions such as the oxidation of hydrogen on Pt nanoparticles, only the outermost surface (exposed surface) contributes substantially to the formation of water. For the system investigated here, the inner surface not substantially contributing to the reaction accounted for at least 70% of the total particle surface as determined from oxygen presaturation experiments of the agglomerate surface. A considerable activity loss of the platinum particles was observed on preheating the nanoparticle agglomerates. The preheating leads to an increase in the nanoparticle size by an order of magnitude due to sintering. It is unclear if this activity reduction is due to changes in the particle surface state or to a real size effect of the nanoparticles.     

The effect of soot particle optical inhomogenity and agglomeration on the analysis of light scattering measurements in flames

Computations have been performed for homogeneous and radially inhomogeneous spheres plus agglomerated structures composed of spherical primary units. The ranges of refractive index and particle size considered are typical of soot in flames. The effects of uncertainty in the refractive index and neglect of its radial distribution on inferring spherical particle sizes and concentrations from in situ light-scattering measurements are delineated. A framework is established for computing various scattering characteristics of agglomerated particles in terms of the scattering functions for spherical particles. The results achieved for agglomerates indicate that mean values of the particle concentration, number of units in an agglomerate and overall agglomerate size may be inferred from light-scattering data.     

Formation of Calcium Carbonate Sub‐Micron Particles in a High Shear Stress Three‐Phase Reactor

The production of precipitated calcium carbonate (PCC) was investigated experimentally under industrially relevant conditions, i.e. at high solid concentrations and increasing amount of solid product in the slurry. Temperature is an important parameter since it determines the crystal structure, the particle shape and, as a consequence, the viscosity of the slurry. Of course, the mass concentration of the raw material also has an important influence on the viscosity. From the particle size distributions of primary particles and agglomerates, it can be concluded that the nucleation process is governed by primary nucleation. Also, heterogeneous nucleation occurs on solid calcium hydroxide particles that are present in the slurry. Especially if the raw material contains impurities heterogeneous nucleation occurs and large and unwanted particles are formed. If the slurry is not stabilized, strong agglomeration occurs that can be influenced by the shear stress introduced to the slurry: a high shear stress which is linked to the viscosity of the slurry limits the upper particle diameter and leads to a steep particle size distribution of the product.     

Experimental data and model predictions of aluminium agglomeration in ammonium perchlorate-based composite propellants including plateau-burning formulations

Sixteen propellant formulations based on ammonium perchlorate (AP), hydroxyl-terminated polybutadiene, and aluminium particles have been tested for size distribution of aluminium agglomerates emerging from their burning surface. The formulations are based on a bimodal size distribution of AP particles. Ten of the formulations exhibit one or two plateaus/mesa in their burning rate variation with pressure (zero/negative pressure exponent of burning rate). The relevant formulation variables, namely, coarse and fine AP sizes and coarse-to-fine ratio, aluminium size and content, and two different curing agents, have been varied. Tests are performed in the 1–10 MPa pressure range. A direct correlation between burning rate and agglomerate size exists for propellants with normal burning rate trends but a neutral or inverse correlation is observed for those exhibiting plateau burning behaviour. Larger the parent aluminium size, lesser the agglomeration, as expected; but the effect of aluminium content is non-monotonic. The coarse AP size influences the aluminium agglomerate size as expected from the pocket model regardless of plateau burning effects. The agglomerate size decreases with increase in fine AP size, however. A computer model developed earlier at this laboratory for prediction of aluminium agglomerates based on three-dimensional packing of particles and deduction of AP particles with attached leading edge diffusion flames is applied to the present formulations. The model under-predicts the agglomerate size, only marginally for propellants that do not exhibit plateau burning rate trends, but substantially, otherwise. This is because it does not take into account effects of binder melt flow and is independent of the curing agent of the binder.     

Effect of the primary particle morphology on the micromechanical properties of nanostructured alumina agglomerates

Depending on the application of nanoparticles, certain characteristics of the product quality such as size, morphology, abrasion resistance, specific surface, dispersibility and tendency to agglomeration are important. These characteristics are a function of the physicochemical properties, i.e. the micromechanical properties of the nanostructured material. The micromechanical properties of these nanostructured agglomerates such as the maximum indentation force, the plastic and elastic deformation energy and the strength give information on the product properties, e.g. the efficiency of a dispersion process of the agglomerates, and can be measured by nanoindentation. In this study a Berkovich indenter tip was used for the characterisation of model aggregates out of sol–gel produced silica and precipitated alumina agglomerates with different primary particle morphologies (dimension of 15–40 nm). In general, the effect of the primary particle morphology and the presence or absence of solid bonds can be characterised by the measurement of the micromechanical properties via nanoindentation. The micromechanical behaviour of aggregates containing solid bonds is strongly affected by the elastic–plastic deformation behaviour of the solid bonds and the breakage of solid bonds. Moreover, varying the primary particle morphology for similar particle material and approximately isotropic agglomerate behaviour the particle–particle interactions within the agglomerates can be described by the elementar breaking stress according to the formula of Rumpf.     

Morphology of single-wall carbon nanotube aggregates generated by electrospray of aqueous suspensions

Airborne single-wall carbon nanotubes (SWCNTs) have a high tendency to agglomerate due to strong interparticle attractive forces. The SWCNT agglomerates generally have complex morphologies with an intricate network of bundles of nanotubes and nanoropes, which limits their usefulness in many applications. It is thus desirable to produce SWCNT aerosol particles that have well-defined, unagglomerated fibrous morphologies. We present a method to generate unagglomerated, fibrous particles of SWCNT aerosols using capillary electrospray of aqueous suspensions. The effects of the operating parameters of capillary electrospray such as strength of buffer solution, capillary diameter, flow rate, and colloidal particle concentration on the size distributions of SWCNT aerosols were investigated. Results showed that electrospray from a suspension of higher nanotube concentration produced a bimodal distribution of SWCNT aerosols. Monodisperse SWCNT aerosols below 100 nm were mostly non-agglomerated single fibers, while polydisperse aerosols larger than 100 nm had two distinct morphologies: a ribbon shape and the long, straight fiber. Possible mechanisms are suggested to explain the formation of the different shapes, which could be used to produce SWCNT aerosols with different morphologies.     

Modeling of surface cleaning by cavitation bubble dynamics and collapse

Surface cleaning using cavitation bubble dynamics is investigated numerically through modeling of bubble dynamics, dirt particle motion, and fluid material interaction. Three fluid dynamics models; a potential flow model, a viscous model, and a compressible model, are used to describe the flow field generated by the bubble all showing the strong effects bubble explosive growth and collapse have on a dirt particle and on a layer of material to remove. Bubble deformation and reentrant jet formation are seen to be responsible for generating concentrated pressures, shear, and lift forces on the dirt particle and high impulsive loads on a layer of material to remove. Bubble explosive growth is also an important mechanism for removal of dirt particles, since strong suction forces in addition to shear are generated around the explosively growing bubble and can exert strong forces lifting the particles from the surface to clean and sucking them toward the bubble. To model material failure and removal, a finite element structure code is used and enables simulation of full fluid–structure interaction and investigation of the effects of various parameters. High impulsive pressures are generated during bubble collapse due to the impact of the bubble reentrant jet on the material surface and the subsequent collapse of the resulting toroidal bubble. Pits and material removal develop on the material surface when the impulsive pressure is large enough to result in high equivalent stresses exceeding the material yield stress or its ultimate strain. Cleaning depends on parameters such as the relative size between the bubble at its maximum volume and the particle size, the bubble standoff distance from the particle and from the material wall, and the excitation pressure field driving the bubble dynamics. These effects are discussed in this contribution.     

Conceptual limitations and extensions of lung-deposited Nanoparticle Surface Area Monitor (NSAM)

Nanoparticle Surface Area Monitor (NSAM, TSI model 3550 and Aerotrak 9000) is an instrument designed to measure airborne surface area concentrations that would deposit in the alveolar or tracheobronchial region of the lung. It was found that the instrument can only be reliably used for the size range of nanoparticles between 20 and 100 nm. The upper size range can be extended to 400 nm, where the minimum in the deposition curves occurs. While the fraction below 20 nm usually contributes only negligibly to the total surface area and is therefore not critical, a preseparator is needed to remove all particles above 400 nm in cases where the size distribution extends into the larger size range. Besides limitations in the particle size range, potential implications of extreme concentrations up to the coagulation limit, particle material (density and composition) and particle morphology are discussed. While concentration does not seem to pose any major constraints, the effect of different agglomerate shapes still has to be further investigated. Particle material has a noticeable impact neither on particle charging in NSAM nor on the deposition curves within the aforementioned size range, but particle hygroscopicity can cause the lung deposition curves to change significantly which currently cannot be mimicked with the instrument. Besides limitations, possible extensions are also discussed. It was found that the tendencies of the particle deposition curves of a reference worker for alveolar, tracheobronchial, total and nasal depositions share the same tendencies in the 20–400 nm size range and that their ratios are almost constant. This also seems to be the case for different individuals and under different breathing conditions. By means of appropriate calibration factors NSAM can be used to deliver the lung deposited surface area concentrations in all these regions, based on a single measurement.     

Elaboration of nanostructured Eu3+-doped Gd2O3 phosphor fine spherical powders using polyol-mediated synthesis

Red-emitting Eu³⁺-doped Gd₂O₃ spherical powders were directly precipitated using a polyol method. The as-synthesized powders consist of agglomerates with a spherical shape and a size ranging between 0.4 and 0.6 μm. Each agglomerate is nanostructured and consists of a packing of nanocrystallites (3–5 nm) of a bcc oxide phase whose luminescence presents original features in comparison with bulk materials. The powders were further calcinated and the size of both crystallites and agglomerates, the crystalline structure and the luminescence were studied as a function of the annealing temperature. For temperatures lower than 900 °C, the samples obtained are highly crystalline and possess the classical Eu³⁺ red luminescence. For optimized temperature, the morphology of the particles can be preserved leading to spherical, dense, luminescent and almost monodisperse oxide powders, 0.5 μm in size. PACS 81.07.Bc; 81.07.Wx; 81.16.Be; 75.50.-y; 42.70.-a     

Carbon phase transformations under electrodynamic compression

The graphite-diamond phase transition under shock-wave-induced electrodynamic compression has been studied. A sample of a carbon-containing material was loaded by axisymmetric collapse of a copper liner. The liner was acted upon by ponderomotive forces generated by pulsed electric currents with amplitudes of 2–4 MA. The collapse of the cylindrical copper liner with a velocity of ∼1 km/s produced stepped loading of the carbon material in an ampoule from 5 to 40 GPa over 4 μs. Purification of the preserved material yielded agglomerates containing polycrystalline diamond. The average size of diamond polycrystals in the agglomerates is 1–2 μm, and the agglomerate yield is ∼3%. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 4, 2004, pp. 659–661. Original Russian Text Copyright ? 2004 by Makarevich, Rakhel, Rumyantsev, Fridman.     

Measurement of Inherent Material Density of Nanoparticle Agglomerates

We describe a new technique to measure the size dependent inherent material density of chain agglomerate particles. Measurements were carried out for diesel soot and aluminum/alumina agglomerate particles in the nanometer size range. Transmission electron microscopy was used to measure the volumes of agglomerate particles that were preselected by mass using an aerosol particle mass analyzer. We found that the density of diesel exhaust particles increased from 1.27 to 1.78g/cm³ as particle mobility size increased from 50 to 220nm. When particles are preheated to remove volatile components, the density was 1.77±0.07g/cm³, independent of particle size. The densities measured after heating correspond to the inherent material density of diesel soot. Measurements with aluminum nanoparticles were made downstream of a furnace where aluminum (Al) was converted to alumina (Al₂O₃). From measurements of inherent material density we were able to infer the extent of reaction, which varied with furnace temperature.     

Analytical characterization of gold nanoparticle primary particles,aggregates, agglomerates,and agglomerated aggregates

Gold nanoparticles have been studied for many biomedical applications. However, alterations in the gold nanoparticles’ environment frequently lead to the formation of aggregates and agglomerates, which have not been well characterized. These new structures could significantly change the biological impact of the nanoparticles, so the appropriate characterization of these structures prior to biological administration is vital for the correct interpretation of toxicology results. By varying the solvent or heating under pressure, four reproducible gold nanoparticles structures were created: 10 nm primary particles, aggregates of the primary particles that contain non-reversible bonds between the individual nanoparticles, agglomerates of primary particles that contain reversible interactions between the individual nanoparticles, and agglomerated aggregates that have reversible bonds linking individual aggregates. Ultraviolet–visible (UV–Vis) spectroscopy, thermal gravitational analysis, and neutron activation analysis were each found to accurately measure the concentration of the primary particles. The primary particles measured 10 nm by dynamic light scattering (DLS) and had a spherical morphology by transmission electron microscopy (TEM) while the aggregates measured 110 nm by DLS and had a distorted morphology by TEM. The agglomerate and aggregated agglomerate samples both measured >1,000 nm by DLS, but the individual particles had significantly different morphologies by TEM. Multiple other analytical techniques, including ultracentrifugation, gel electrophoresis, and X-ray diffraction, also showed unique traits for each structure. The structural differences did not change in the presence of cell culture media or rat serum. In addition, the primary particles, aggregates, and agglomerates each had a unique UV–Vis spectrum, allowing for an inexpensive, rapid method to differentiate between the structures.     

Production of cobalt and nickel particles by hydrogen reduction

Cobalt and nickel nanoparticles were produced by hydrogen reduction reaction from cobalt or nickel chloride precursor vapour in nitrogen carrier gas. This aerosol phase method to produce nanoparticles is a scalable one-step process. Two different setups were introduced in particle production: a batch type reactor and a continuously operated reactor. Common feature in these setups was hydrogen mixing in a vertical flow reactor. The process was monitored on-line for particle mass concentration and for gas phase chemical reactions. Tapered element oscillating microbalance measured the particle mass concentration and Fourier transform infrared spectroscopy was used to monitor relevant gas phase species. The produced cobalt and nickel particles were characterised using transmission electron microscopy and x-ray diffraction. The produced cobalt and nickel particles were crystalline with cubic fcc structure. Twinning was often observed in cobalt particles while nickel particles were mostly single crystals. The cobalt particles formed typically long agglomerates. No significant neck growth between the primary particles was observed. The primary particle size for cobalt and nickel was below 100 nm.     

Agglomeration of particles by a converging ultrasound field and their quantitative assessments

The acoustic radiation force resulting from acoustic waves have been extensively studied for the contact-free generation of organized patterning arrays. The precise arrangement of microscopic objects clustered at the pressure nodes is critical to the development of functional structures and patterned surfaces. However, the size of the clusters is restricted by the saturation limit of the acoustic nodes. Here, we present a bulk acoustic wave (BAW) platform, which employs a two-dimensional acoustic wave to propel particles of various sizes. Experimentally, when particles are large, significant acoustic energy is scattered and partly absorbed by the matched layers in front of the sensors. The acoustic radiation force from a convergent acoustic pressure field agglomerates the large polystyrene (PS) particles towards the central region instead of the pressure nodes. The parametric analysis has been performed to assess the transition in the particles from clustering at the organized nodal arrays to agglomerating in the central region, which is a function of particle size, particle concentration, and load voltage. Statistically, the particles can agglomerate with a cluster ratio greater than 70%, and this ratio can be improved by increasing the load power/voltage supplied to the transducers. With its ability to perform biocompatible, label-free, and contact-free self-assembly, this concept offers a new possibility in the fabrication of colloidal layers, the recreation of tissue microstructure, the development of organoid spheroid cultures, the migration of microorganisms, and the assembly of bioprinting materials.     

Simulation of nanopowder compaction in terms of granular dynamics

The uniaxial compaction of nanopowders is simulated using the granular dynamics in the 2D geometry. The initial arrangement of particles is represented by (i) a layer of particles executing Brownian motion (isotropic structures) and (ii) particles falling in the gravity field (anisotropic structures). The influence of size effects and the size of a model cell on the properties of the structures are studied. The compaction of the model cell is simulated with regard to Hertz elastic forces between particles, Cattaneo-Mindlin-Deresiewicz shear friction forces, and van der Waals-Hamaker dispersion forces of attraction. Computation is performed for monodisperse powders with particle sizes ranging from 10 to 400 nm and for “cohesionless” powder, in which attractive forces are absent. It is shown that taking into account dispersion forces makes it possible to simulate the size effect in the nanopowder compaction: the compressibility of the nanopowder drops as the particles get finer. The mean coordination number and the axial and lateral pressures in the powder systems are found, and the effect of the density and isotropy of the initial structure on the compressibility is analyzed. The applicability of well-known Rumpf’s formula for the size effect is discussed.