Formation Of Primary Particles Research Articles

Soot primary particle formation from multiscale coarse-grained molecular dynamics simulation

A new multiscale coarse-graining procedure is used to study carbonaceous nanoparticle agglomeration in combustion environments. The computational methodology is applied to an ensemble of 10,000 nanoparticles (or effectively 2 million total carbon atoms) to simulate, for the first time, the agglomeration of carbonaceous nanoparticles using coarse-grained atomistic-scale information. In particular, with the coarse-graining approach we are able to assess the influence of nanoparticle morphology and temperature on the agglomeration process. The coarse-graining of the interparticle force field is accomplished applying a force-matching procedure to data obtained from trajectories and forces from all-atom MD simulations. The coarse-grained MD results show rich and varied clustering behaviors for different particle morphology and, in some cases, the formation of primary particles with a diameter around 15 nm are observed for the first time by molecular simulation techniques.

Fabrication of Hollow Inorganic Microspheres by Chemically Induced Self-Transformation

Two contrasting approaches, involving either polymer-mediated or fluoride-mediated self-transformation of amorphous solid particles, are described as general routes to the fabrication of hollow inorganic microspheres. Firstly, calcium carbonate and strontium tungstate hollow microspheres are fabricated in high yield using sodium poly(4-styrenesulfonate) as a stabilizing agent for the formation and subsequent transformation of amorphous primary particles. Transformation occurs with retention of the bulk morphology by localized Ostwald ripening, in which preferential dissolution of the particle interior is coupled to the deposition of a porous external shell of loosely packed nanocrystals. Secondly, the fabrication process is extended to relatively stable amorphous microspheres, such as TiO2 and SnO2, by increasing the surface reactivity of the solid precursor particles. For this, fluoride ions, in the form of NH4F and SnF2, are used to produce well-defined hollow spheroids of nanocrystalline TiO2 and SnO2, respectively. Our results suggest that the chemical self-transformation of precursor objects under morphologically invariant conditions could be of general applicability in the preparation of a wide range of nanoparticle-based hollow architectures for technological and biomedical applications.

The microstructural characterization of semi-solid slurries

Due to recent interest in semi-solid metal (SSM) processing, there is a need for fundamental knowledge on the formation and solidification of primary particles. The primary particle size, distribution, morphology, and percentage are the main concerns because particle quantity and size affect not only the mechanical properties of as-cast SSM parts but also the flow characteristics of SSM slurries during die filling. Microstructural characterization is a basic tool for measuring the critical parameters that influence the resulting properties. This article describes the tools and techniques available for structural analysis of SSM slurries. It also attempts to elucidate the ambiguities and interpretations of special structural features.

Creation of semisolid slurries containing fine and spherical particles by grain refinement based on the Mullins–Sekerka stability criterion

A non-agitation liquid processing approach for the production of semisolid magnesium slurries containing fine and spherical particles has been proposed on the basis of the Mullins–Sekerka stability criterion for spherical growth and recent advances in grain refinement of magnesium. It is shown that semisolid magnesium slurries containing fine and spherical particles are obtainable directly from the liquid state without agitation, via effective control of nucleation and growth by grain refinement with zirconium. The solid fraction can be varied in a wide range up to more than 50%. The formation of spherical primary magnesium particles is attributed to the combined effects of both dissolved and undissolved zirconium, which give rise to a high nucleation rate and a small undercooling when the melt contains a high level of dissolved zirconium and a sufficient number of suitably sized, undissolved zirconium particles. Grain refinement offers a promising non-agitation liquid processing approach for semisolid structure formation.

Synthesis and Characterization of 0.9PMN-0.1PT Powders by the Use of a Modified Columbite Precursor

The complex perovskite compound 0.9PbMg1/3Nb2/3O3-0.1PbTiO3 is one of the most promising relaxor ceramic because the addition of lead titanate increases Tm by about 5°C/mol% from intrinsic Tm value for pure PMN (near –7 to -15°C). A Ti-modified columbite precursor was used to prepare PMN-PT powders containing single perovskite phase. This variation on columbite route includes Ti insertion in MgNb2O6 orthorhombic structure so that individual PT synthesis becomes unnecessary. Furthermore, effects of Li additive on columbite and PMN-PT structures were studied by XRD to verify the phase formation at each processing step. XRD data were also used for the structural refinement by Rietveld method. The additive acts increasing columbite powders crystallinity, and the amount of perovskite phase was insignificantly decreased by lithium addition. By SEM micrographs it was observed that Li presence in PMN-PT powders leads to the formation of rounded primary particles and for 1mol% of additive, the grain size is not changed, different from when this concentration is enhanced to 2mol%.

Efficient Low-Temperature Oxidation of Carbon-Cluster Anions by SO2

Carbon-cluster anions, CN-, are very reactive toward SO2 (sticking probability of 0.012 +/- 0.005 for C27- at 25 degrees C), in contrast to their inertness toward other common atmospheric gases and pollutants. In flow reactor experiments at ambient temperature and near atmospheric pressure, primary adsorption of SO2 by the carbon cluster anions, N = 4-60, yields CNSO2- or CN-1S-. The inferred elimination of neutral CO2 is also detected as meta-stable decay in collision-induced dissociation. At higher temperatures, the reaction of SO2 with nascent carbon clusters yields CN-1SO- as well as undetected CO. The size-dependent initial reactivity reflects the previously established structural transitions (i.e., from chain to cyclic to cage structures). Such carbon clusters are formed in sooting flames and may act as nuclei for the formation of primary soot particles and serve as models for the local structural features of active soot particle sites for black-carbon soot. The facile generation of reactive carbon-sulfide and -sulfinate units may therefore have implications for understanding the health and environmental effects attributed to the coincidence of soot and SO2.

Morphologies of Large-Pore Periodic Mesoporous Organosilicas

In this article, we report a systematic investigation on the morphologies of SBA-15 type large-pore periodic mesoporous organosilicas templated by the block copolymer P123. By tuning synthetic parameters such as stirring, acidity, reaction ratio, reaction duration, and autoclaving, a wide spectrum of unique primary particle morphologies, such as the spindle-, pearl-, diamond-, rod-, and platelike particles, and nanoparticles has been prepared. These primary particles were found to self-assemble in solution to form various large hierarchical macrostructures, such as mesostructured necklaces and cobweb-supported necklaces. The assembling process was elucidated with the information observed at different stages of reaction. Stirring, reaction duration, and autoclaving were identified to be the key factors affecting the efficiency and degree of the self-assembly process. A nucleation-accretion mechanism for the formation of various PMO primary particles was proposed by examining the relation between the external morphologies and the underlying mesostructure.

Particle features of a poly(methyl methacrylate) resin prepared by a new emulsion polymerization process

A new emulsion polymerization process, in which water acted as the dispersed phase and a mixture of methyl methacrylate (MMA) and cyclohexane acted as the continuous phase, was applied to the preparation of a poly(methyl methacrylate) (PMMA) resin. The primary (latex) particles were formed in the early stage of polymerization and coagulated as the polymerization conversion increased. Scanning electron micrographs showed that the final PMMA particles were porous and composed of loosely aggregated primary particles. The porosity characterized by cold di(2-ethylhexyl) phthalate absorption increased as the water/oil and cyclohexane/MMA mass ratios increased. The PMMA primary particles were smaller than the primary particles in the PMMA resin prepared by suspension polymerization in the presence of cyclohexane. Because of the phase composition of the reaction system, the solubility of PMMA in a mixture of cyclohexane and MMA, and the particle morphology of PMMA, a particle formation mechanism, including the formation, growth, and coagulation of primary particles in dispersed water droplets, was proposed. The primary particles formed mainly through a homogeneous nucleation mechanism and increased in size as MMA diffused from the oil phase to the water phase to the primary particles. The coagulation of the primary particles occurred because of the lower colloidal stability and the space limitations of the primary particles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1905–1911, 2004

Fine and ultrafine particles in the Zürich (Switzerland) area measured with a mobile laboratory: an assessment of the seasonal and regional variation throughout a year

Abstract. On occasion of the project YOGAM (year of gas phase and aerosol measurements), the spatial and temporal variation of selected aerosol and gas phase parameters was assessed for the Zürich (Switzerland) area with a new mobile pollutant measurement laboratory. This assessment based on on-road measurements along a specified route on selected days during different seasons in 2001/2002, covering urban, suburban and rural regions. Special focus was put on the investigation and characterization of particles in the fine (particle diameter D<2.5 mm) and ultrafine (D<100 nm) size ranges. Analysis of Variance (ANOVA) showed that the variance of all considered fine and ultrafine aerosol parameters (i.e. particle background and total number concentration for particles larger than 3 nm, number concentrations in the size ranges 7-30 nm and 80-140 nm, as well as the active surface area concentration) was significantly larger for day-to-day than for spatial variation. However, Principal Component Analysis (PCA) found a similar regional pollution pattern within every single measuring day. Lowest particle background levels (D>3 nm) were found in rural areas at higher elevation (15 000 cm-3), while corresponding mean background values for urban and freeway-influenced areas were typically 35 000 cm-3 and >80 000 cm-3, respectively. Meteorology, i.e. prevailing weather conditions not only governed the day-to-day concentration variations in the selected area, but also influenced the formation of primary (directly traffic-related) and in few cases secondary (biogenic or anthropogenic) ultrafine particles. Overall, low temperatures regularly enhanced primary ultrafine particle formation in urban areas. There was a possible indication for relatively low number concentrations of secondary ultrafine particles during a few warm and sunny spring days. Mobile measurements as they were performed in this study have been shown to be suitable for pollutant assessments to obtain good information on spatial and day-to-day variability. For experimental studies concerning spatial resolution on a relatively short time scale (<1 day), a mobile measurement design may even be more appropriate than a network of stationary measuring sites.

Primary particle formation from vehicle emissions during exhaust dilution in the roadside atmosphere

Abstract Measurements of particle number size distribution in the range 11–452 nm have been made on the side of the busy Marylebone Road in central London over a period from April 1998 to August 2001. The data have been analysed to demonstrate the influences of meteorological factors upon different size fractions and upon the overall size distribution. The relationship to traffic volumes indicates that the accumulation mode particles are associated with emissions from heavy-duty traffic (mainly diesel vehicles) whilst particles in the range 30–60 nm show a stronger association with light-duty traffic. Both of these size fractions show the anticipated dilution effect with increasing wind speed. Particles in the 11–30 nm range behave anomalously showing no clear relationships to traffic volumes and a lesser effect of dilution by increasing wind speed than for the larger particles. Particles in this fraction tend to peak in the early morning showing an inverse association with air temperature. It is concluded that this size range contains freshly nucleated particles formed as the exhaust gases are diluted with ambient air.

Fumed silica synthesis. Influence of hydrogen chloride on the fumed silica particle formation process

AbstractInteraction of silicon dioxide molecule up to the small silica protoparticle and primary particle formation, and influence of hydrogen chloride (HCl), water (H2O) and inert molecules (nitrogen N2) “under flame condition” and “after cooling” on structure and properties of fumed silica were investigated by quantum‐chemical simulations. An attempt to give definition of surface concept on atomic level was made.

Monodispersed spindle-type goethite nanoparticles from FeIII solutions

A new synthetic route for producing monodispersed and single crystal acicular goethite particles with small particle size and a high axial ratio adequate for use as a high density magnetic recording media precursor is reported. It essentially consists of the hydrolysis of alkaline FeIII suspensions in the presence of carbonate by a three-step procedure, the formation of ferrihydrite primary particles, the ferrihydrite dissolution and nucleation of goethite, and the growth of the goethite nuclei. Changing the temperature of heating during ageing achieved a separation of the two last stages. X-Ray diffraction, transmission electron microscopy, infrared spectroscopy and surface area data have been used to determine the mechanism responsible for the formation of goethite particles with controlled size and shape. The best conditions to prepare monodispersed goethite particles have been established. The results show that uniform goethite particles of (a) 60 nm length with an axial ratio of 6 and (b) 230 nm length with a high axial ratio of 10, can be obtained by using an [OH]/[Fe] molar ratio of 0.35 in the initial suspensions with carbonate or sodium hydroxide, respectively. The [OH]/[Fe] molar ratio determines the particle size and elongation by controlling the hydrolysis reaction rate, while the carbonate ions promote a constant [OH] in the solution, keeping the pH around 10 during the entire synthesis process. This procedure, associated with the appropriate temperature control, leads, under certain conditions, to highly homogeneous goethite particles with sizes smaller than those obtained using sodium hydroxide with the same [OH]/[Fe] ratio.

Fine-stranded and particulate aggregates of heat-denatured whey proteins visualized by atomic force microscopy.

beta-Lactoglobulin and whey protein isolate (WPI) were heated in aqueous solutions at pH 2 and 7 at 80 degrees C, spread onto freshly cleaved mica surfaces, and visualized under butanol using atomic force microscopy. Fine-stranded aggregates were formed at pH 2, the diameter of strands being ca. 4 nm for beta-lactoglobulin and 10 nm for WPI. At pH 7, aggregates were composed of ellipsoidal particles, regardless of the concentration of added NaCl. This observation supports the previously proposed two-step aggregation model at neutral pH (Aymard, P.; Gimel, J. C.; Nicolai, T.; Durand, D. J. Chim. Phys. 1996, 93, 987-997), consisting of the formation of primary globular particles and the subsequent aggregation of those primary particles. The AFM provides the first direct evidence for the anisotropic shape of these primary particles. The heights of primary particles increased from ca. 11 to 27 nm with increasing concentrations of added NaCl from 0 to 0.3 M in the case of WPI. The rate of aggregation was also accelerated with increasing NaCl concentrations, which appeared to induce transitions in gel networks from fine-stranded toward particulate networks. The present study provides structural information essential for understanding the diverse physical properties of heat-induced whey protein gels.

Control of Primary Particle Size and the Onset of Aggregate Formation: The Effect of Energy Release in Nanoparticle Collision and Coalescence Processes

AbstractDuring coalescence, the surface area of the particle decreases, resulting in a heat release associated with the resulting lower surface energy. In a growth process particle heating competes with heat transfer by conduction to the cooler carrier gas and radiation. This temperature increase can be extremely important and should be accounted for when modeling collision/coalescence processes. The heat release associated with particle coalescence may reduce the coalescence time by as much as a few orders of magnitude. In addition, under some conditions there is insufficient time for the particles to cool to the gas temperature before another collision event takes place. It is shown that accounting for energy release and heat transfer effects have a dramatic effect on primary particle formation and the onset of aggregate formation. The results of the work indicate that to grow the largest primary particles one should operate at low pressures and high volume loadings.

Energy accumulation in nanoparticle collision and coalescence processes

During coalescence, the surface area of the particle decreases, resulting in a heat release associated with the resulting lower surface energy. In a growth process particle heating competes with heat transfer by conduction to the cooler carrier gas and radiation. This temperature increase can be extremely important and should be accounted for when modeling collision/coalescence processes. The heat release associated with particle coalescence may reduce the coalescence time by as much as a few orders of magnitude. In addition, under some conditions there is insufficient time for the particles to cool to the gas temperature before another collision event takes place. Two such cases are investigated in this paper: (1) low pressure growth of Si nanoparticles and (2) high volume loading growth of TiO 2 nanoparticles. It is shown that accounting for energy release and heat transfer effects have a dramatic effect on primary particle formation and the onset of aggregate formation. The results of the work indicate that to grow the largest primary particles one should operate at low pressures and/or high volume loadings.

Fumed silica synthesis: influence of small molecules on the particle formation process

Burning silicon tetrachloride in an oxygen-hydrogen flame produces fumed silica. This process is known for at least 50 years [1-5], but some important details are still uncertain. We would like to study several starting steps of fumed silica synthesis on the way from molecules to products. To do this we have performed quantum-level simulations of protoparticle and primary particle formation, from silicon dioxide molecules. Additionally, we have simulated the behavior of silica clusters in the presence of small molecules like water and hydrochloric acid. The reaction of silicon dioxide molecules leads to a silica cluster, which is covered with chemicaly highly active sites of one-coordinated oxygen atoms and three-coordinated silicon atoms. These clusters interact together and produce silica bulk like quartz glass. Reaction with water terminates the silica particle surface and leads to a complicated structure of the particle surfaces. The hydroxyl shell protects the particle body against the increase in particle size, but leads to aggregate and agglomerate formation.

Carbon Black and Fullerenes: New Discoveries in Early Formation Mechanisms and Nucleation

Abstract Recent studies on the formation of carbon black have resulted in the previously unreported finding of buckminster-fullerene, C60, in trace quantities in the toluene extractable materials. High-resolution transmission electron microscopy (HRTEM) experiments indicate the molecule may be functioning as a nucleation site in the formation of primary particles of carbon black. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) provided the surface chemical analysis of conventional and experimental carbon blacks. The toluene extracts represented the precursor compounds present in the gaseous phase at the time of quench. The extracts were analyzed by Fourier transform infrared (FTIR) spectroscopy, liquid chromatography (LC)/mass spectroscopy (MS) and elemental composition. The data, taken as a whole, have led to a more clear understanding of the competitive chemical pathways occurring during the inception and nucleation of a primary particle of carbon black. Direct observation of nucleation sites and types are possible with HRTEM analysis.

Monodisperse micron-sized cross-linked polystyrene particles. VI. Understanding of nucleated particle formation and particle growth

The procedure of nucleated particle formation and particle growth in dispersion polymerization was studied with the intention of understanding the production of monodisperse polystyrene particles cross-linked with urethane acrylate (UA). The time required for the formation of primary particles was determined exactly from the turbidity measurement of the reaction mixture with the polymerization time. It could be found that differing from conventional divinyl cross-linkers, such as divinylbenzene, UA had a boundary concentration where the association and coagulation of preformed nuclei with other oligomers and/or nuclei effectively took place until the primary particle formed. Similarly to linear polystyrene particles, the particle number density of the primary particles cross-linked with UA remained constant to the final particles. This observation verifies the suggestion that the primary particles cross-linked with UA readily absorbed the monomers from the medium during the stage of particle growth.

Unseeded semibatch emulsion polymerization of butyl acrylate: Bimodal particle size distribution

Unseeded semibatch emulsion polymerization of butyl acrylate (BA) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator was carried out at the conditions where secondary nucleation was probable. This was achieved by using no emulsifier in the initial reactor charge. The effects of changes in monomer emulsion feed rate, initiator concentration and distribution, emulsifier concentration in the feed, and temperature on the evolution of particle size averages and distribution were investigated. Bimodal particle size distributions (PSD) were obtained for most of the latexes. Inhibition effects were found to be important in the development of PSD. Primary particle formation occurred through micellar nucleation, whereas secondary nucleation probably occurred through homogenous nucleation. The polydispersity index (PDI) of the latexes increased with the decreasing monomer emulsion feed rate. The application of a larger amount of initiator to the reactor charge or using a higher temperature, reduced the formation of secondary particles and resulted in a formation of an unimodal PSD. The overall steady-state rate of polymerization was found to approach the rate of monomer addition (Rp ≈ Ra ), if the emulsifier concentration in the aqueous phase was appreciable. This is different from the correlation 1/Rp = 1/K + 1/Ra obtained for the BA semibatch process with neat monomer feed. This suggests that different rate expressions can be used for BA semibatch emulsion polymerization at different conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 528–545, 2000

Preparation of high acicular and uniform goethite particles by a modified-carbonate route

A procedure for the synthesis of high acicular and uniform goethite particles based on a modified-carbonate route is reported. It essentially consists of the oxidation–precipitation of iron sulfate solutions through a two-oxidation process, which involves the formation of primary particles and their subsequent growth. XRD, TEM, colour evolution and pH monitoring have been used to determine the mechanism responsible for the formation of goethite particles with well-controlled morphology. Single-phase goethite particles are formed from initial suspensions with OH/Fe equivalent ratios from 0.05 to 0.35, which determine the supersaturation level of the solution and consequently, the length of the particles. The best conditions to prepare uniform goethite particles of 250 nm in length and high axial ratio (8), adequate as high-density audio/video media precursors, have been established.