Fragmentation in oblique impaction for nanoparticle-agglomerates with different structures

Impact fragmentation can be used to disperse nanoparticle-agglomerates. While the fragmentation of openly structured (fractal dimension D_f?<?2) agglomerates during perpendicular impaction was the subject of several investigations, the fragmentation during oblique impaction is not experimentally investigated so far. During oblique impaction a tangential velocity component acts on the agglomerates leading to an increased fragmentation for the investigated agglomerate structures (with D_f?=?1.6, 1.8, 2.3, 2.6 and 3.0). For the agglomerates with D_f?=?1.6. 1.8, 2.3 and 2.6 the degree of fragmentation can be described with the Weibull-statistics using the tangential impact velocity. This shows that the fragmentation during oblique impaction is determined by the tangential velocity component. The reason for the differing behavior of spherical agglomerates could not be elucidated but it is hypothesized, that a transition from sliding to rolling during the impact occurs affecting the fragmentation behavior.The breakage pattern is obtained by analyzing the fragment size distribution as a function of the impact energy. For agglomerates with fractal dimensions of D_f?=?1.6, 1.8, 2.3 and 2.6 a broad size distribution is observed containing small clusters/primary particles, bigger fragments and intact agglomerates at low impact energies. Increasing the impact energy shifts the whole fragment size distribution to smaller sizes. A nearly total disintegration at high impact energies is reached. The spherical agglomerates fracture into nearly equal sized fragments resulting in a narrower size distribution, which is shifted to smaller sizes at higher impact energies.     

Agglomerates and aggregates of nanoparticles made in the gas phase

Gas-phase (aerosol) technology is used widely in manufacture of various nanostructured commodities at tons/hour today. So it is quite promising for synthesis of sophisticated nanoparticles motivating basic and applied research. Frequently such nanoparticles are made as clusters of primary particles (PPs) by chemical reaction, aerosol coagulation, sintering, surface growth and even fragmentation. When PPs are bonded by strong chemical forces, they are termed aggregates. As such they are sought in catalysis, lightguide preform manufacture and, most importantly, as components in electronic devices (sensors, batteries). When PPs and aggregates are held together by rather weak, physical forces, they form agglomerates. These are attractive in nanocomposites and fluid suspensions (paints, nanofluids, bioimaging). Such clusters may have also distinct health effects, beyond those of equivalent spherical particles.Agglomerates and aggregates are characterized by microscopy, electromagnetic scattering and mass mobility measurements in terms of their volume-equivalent radius, radius of gyration and/or mobility radii in the free molecular and continuum regimes along with the corresponding power laws (fractal dimension, D_f). Coagulation and sintering largely determine nanoparticle structure. Coagulation of PPs leads to agglomerates of D_f = 1.78 and 1.91 in the continuum and free-molecular regimes, respectively. The coagulation rate of agglomerates is higher than that of volume-equivalent spheres in the free molecular regime. Agglomerates attain also a self-preserving size distribution by coagulation facilitating process design for their manufacture. Mesoscale simulations elucidate the sintering (or coalescence) of agglomerates to aggregates and narrowing of their PP size distribution. Once agglomerates start to sinter, they follow a power law to aggregates and eventually to compact (spherical) particles, regardless of composition and initial PP size distribution. Aggregate properties are in-between those of the initial agglomerate and the fully coalesced sphere. Finally the stability of agglomerates under ultrasonication, stretching, fluid dispersion, impaction and capillary condensation is highlighted.     

Estimation of agglomerate size of multi-walled carbon nanotubes in fluidized beds

The objective of this study was to determine hydrodynamic characteristics of multi-walled carbon nanotubes (MWCNTs) agglomerates and examine their sizes. The bed collapsing process of MWCNTs agglomerates was found to be closer to that of Geldart group C particles than group A particles. Median diameters of MWCNTs agglomerates determined by sedimentation method at initial superficial gas velocity of 0.120 and 0.190 m/s were 157 and 221 μm, respectively. The size of these MWCNTs agglomerates in fluidization state was measured by image analysis using a high speed camera. Median diameters of these MWCNTs agglomerates in freeboard were increased from 138 to 189 μm as superficial gas velocity was increased from 0.088 to 0.190 m/s at static bed height of 0.16 m. Median diameter and size distribution determined by sedimentation method fitted well with those measured using image analysis. Results were reasonable at superficial gas velocity up to 0.190 m/s.     

Particle size distribution control and related properties improvements of tungsten powders by fluidized bed jet milling

Fine grinding process of different particle size tungsten powders was carried out by fluidized bed jet milling. The results showed that the jet milling treatment caused deagglomeration of tungsten powders, which led to particles sufficient dispersion and narrow particle size distribution. Grinding gas pressure of 0.70 Mpa made the particles achieve high speed which promoted the particles collision contributing to particle dispersion and shape modification. For tungsten powder with particle size of 3 μm FSSS, a higher packing density with 5.54 g/cm³ was obtained, compared with the 3.71 g/cm³ of the original powder. For tungsten powder with particle size of 1 μm FSSS, the big agglomerates disappeared and the particle size distribution become narrower, while small aggregates about 2–3 μm still exist after the jet milling process. For tungsten powder with particle size of 5 μm and 10 μm FSSS, different medium diameter particle size and narrow particle size distribution of monodisperse tungsten powders can be produced by the optimized jet milling parameters. More important, the effective dispersion, favorable shape modification and precise classification have been achieved in the simple process.     

Formation of ZnS nano- and microparticles from thiourea solutions

Effects of temperature, concentration of thiourea and reaction conditions (thermal heating and microwave irradiation) on morphological properties of ZnS particles obtained by sedimentation from 0.01, 0.1 and 1 М zinc nitrate solutions are studied. It is found that ZnS particles of two shapes are formed from thiourea solutions at a thermal heating (70–90 °С): agglomerated particles of the spherical shape with the dimensions of agglomerates 50–100 nm (particle size in agglomerates of 3–5 nm) and hexagonal columns in length up to 2 μm and diameter of 80–100 nm. At the microwave heating conditions (90 °С), irrespective of thiourea concentration formation of spherical ZnS particles with the size 0.6–1.2 μm is observed.     

Contact properties determination of macroscopic fine disperse glass particles via compression tests in normal direction

The paper describes the deformation behavior of spherical, dry and non-porous particles during a single particle compression test in normal direction. Therefore a compression tester was built. Industrial used soda lime glass particles with two macroscopic fine disperse sizes (d_1,50,3 = 284.30 μm and d_2,50,3 = 513.20 μm) were applied as model material to investigate the micromechanical contact behavior. In order to influence the elastic-plastic contact properties of particles, the surfaces were altered with chemical modification by means of silanization.The determination of various micromechanical contact properties (e.g. adhesion force, modulus of elasticity and contact stiffness) was carried out model-based with the contact model ‘stiff particles with soft contacts’ by means of a back-calculation.It could be shown that the model-based determination of material properties was a good alternative compared to the comprehensive tensile tests and pull-off force measurements.In addition to the gained normal force-displacement data in normal direction, the friction limits for tangential loading and rolling with the load-dependent adhesion force were model-based determined.     

Lattice Boltzmann simulation of flow past a non-spherical particle

Lattice Boltzmann method was used to predict the fluid-particle interaction for arbitrary shaped particles. In order to validate the reliability of the present approach, simulation of flow past a single stationary spherical, cylindrical or cubic particle is conducted in a wide range of Reynolds number (0.1 < Re_p < 3000). The results indicate that the drag coefficient is closely related to the particle shape, especially at high Reynolds numbers. The voxel resolution of spherical particle plays a key role in accurately predicting the drag coefficient at high Reynolds numbers. For non-spherical particles, the drag coefficient is more influenced by the particle morphology at moderate or high Reynolds numbers than at low ones. The inclination angle has an important impact on the pressure drag force due to the change of projected area. The simulated drag coefficient agrees well with the experimental data or empirical correlation for both spherical and non-spherical particles.     

Size-controlled hydrothermal synthesis of monodispersed BaZrO3 sphere particles by seeding

Monodispersed barium zirconate (BaZrO₃) fine particles with a spherical shape have been synthesized by hydrothermal reactions using barium hydroxide and a Zr-triethanolamine (TEOA) complex. The particle mean diameter was gradually controlled in a range from 0.20 μm to 3.5 μm by change in the added amount of seed nanoparticles. The mechanistic characterization of the seed-mediated BaZrO₃ sphere synthesis revealed that the particle growth obeyed a simple seed growth mechanism. In the present system, utilization of the Zr-TEOA complex played an important rule to prevent uncontrollable nucleation to form the uniform BaZrO₃ fine particles with narrow size distributions.     

Impact of precursor solution concentration to form superparamagnetic MgFe2O4 nanospheres by ultrasonic spray pyrolysis technique for magnetic thermotherapy

The superparamagnetic magnesium ferrite (MgFe₂O₄) dense nanospheres are synthesized by ultrasonic spray pyrolysis (USP) method from different concentrations of the initial precursor solution. The effect of precursor solution concentration on the particle’s size, morphology, and superparamagnetic behavior has been investigated. XRD results confirm that studied precursor concentration (0.06, 0.12 and 0.24 M) exhibited single phase cubic structure. The mean crystallites size (called as primary particles) of 0.06, 0.12 and 0.24 M samples are 9.6, 11.5, 11.0 nm, respectively but the entire nanosphere’s diameter (called as secondary particles) increases from 206 to 340 nm with increasing precursor concentration. TEM analysis also reveals that nanospheres consist of densely aggregated crystallites of spherical shape and smooth surface. The value of polydispersity index (PDI) shows narrower size distribution for lower concentration. Magnetic properties indicate the superparamagnetic nature for all samples. Herein, the appropriate induction heat generation rate with better morphology was obtained for 0.06 M concentration. Ion release in the aqueous solution of the composition (about 95% for Mg; 99% for Fe) indicating better stability has been confirmed by ICP-OES test. In this approach, as-synthesized nanospheres are suitable for using as a heating agent in magnetic thermotherapy application.     

Analysis of triboelectric charging of particles due to aerodynamic dispersion by a pulse of pressurised air jet

Triboelectric charging of powders causes nuisance and electrostatic discharge hazards. It is highly desirable to develop a simple method for assessing the triboelectric charging tendency of powders using a very small quantity. We explore the use of aerodynamic dispersion by a pulse of pressurised air using the disperser of Morphologi G3 as a novel application. In this device particles are dispersed by injection of a pulse of pressurised air, the dispersed particles are then analysed for size and shape analysis. The high transient air velocity inside the disperser causes collisions of sample particles with the walls, resulting in dispersion, but at the same time it could cause triboelectric charging of the particles. In this study, we analyse this process by evaluating the influence of the transient turbulent pulsed-air flow on particle impact on the walls and the resulting charge transfer. Computational Fluid Dynamics is used to calculate particle trajectory and impact velocity as a function of the inlet air pressure and particle size. Particle tracking is done using the Lagrangian approach and transient conditions. The charge transfer to particles is predicted as a function of impact velocity and number of collisions based on a charge transfer model established previously for several model particle materials. Particles experience around ten collisions at different velocities as they are dispersed and thereby acquire charges, the value of which approaches the equilibrium charge level. The number of collisions is found to be rather insensitive to particle size and pressure pulse, except for fine particles, smaller than about 30 µm. As the particle size is increased, the impact velocity decreases, but the average charge transfer per particle increases, both very rapidly. Aerodynamic dispersion by a gas pressure pulse provides an easy and quick assessment of triboelectric charging tendency of powders.     

Low-temperature ultrasound synthesis of nanocrystals CoTiO3 without a calcination step: Effect of ultrasonic waves on formation of the crystal growth mechanism

CoTiO₃ nanocrystallites with an average diameter of 50 nm were synthesized successfully by the sonochemical method without a calcination step and using C₁₀H₁₆N₂O₈ (EDTA) as the chelating agent. To reach an in-depth understanding of the scientific basis of the proposed process, an in-detail analysis was carried out for characterization of nanoscale CoTiO₃ particles via XRD, FTIR, FE-SEM and UV–vis diffuse reflectance spectroscopy (DRS). The crystallite size, average particle size and band gap are found to be 10.7 nm, in the range of 50 nm and 4.64 eV, respectively. The mechanism and the formation process of CoTiO₃ in the sonochemical process were proposed. It was found that nanocrystals were formed directly before being oriented and aggregated into large particles in aqueous solution under ultrasonic irradiation. The nucleation in the sonocrystallization process was accelerated by the implosive collapse of bubbles, while the crystal growth process was inhibited or delayed by shock waves and turbulent flow created by ultrasonic radiation. A pure complex perovskite phase of spherical shape was formed completely in a short irradiation time without the calcination process. Sonochemical irradiation could accelerate spherical shape formation of the particles significantly. These results provide new insights into the development and design of better nanomaterial synthesis methods.     

Investigation of thermal conductivity and dielectric properties of LDPE-matrix composites filled with hybrid filler of hollow glass microspheres and nitride particles

The hybrid filler of hollow glass microspheres (HGM) and nitride particles was filled into low-density polyethylene (LDPE) matrix via powder mixing and then hot pressing technology to obtain the composites with higher thermal conductivity as well as lower dielectric constant (D_k) and loss (D_f). The effects of surface modification of nitride particles and HGMs as well as volume ratio between them on the thermal conductivity and dielectric properties at 1 MHz of the composites were first investigated. The results indicate that the surface modification of the filler has a beneficial effect on thermal conductivity and dielectric properties of the composites due to the good interfacial adhesion between the filler and matrix. An optimal volume ratio of nitride particles to HGMs of 1:1 is determined on the basis of overall performance of the composites. The thermal conductivity as well as dielectric properties at 1 MHz and microwave frequency of the composites made from surface-modified fillers with the optimal nitride to HGM volume ratio were investigated as a function of the total volume fraction of hybrid filler. It is found that the thermal conductivity increases with filler volume fraction, and it is mainly related to the type of nitride particle other than HGM. The D_k values at 1 MHz and microwave frequency show an increasing trend with filler volume fraction and depend largely on the types of both nitride particles and HGMs. The D_f values at 1 MHz or quality factor (Q × f) at microwave frequency show an increasing or decreasing trend with filler volume fraction and also depend on the types of both nitride particle and HGM. Finally, optimal type of HGM and nitride particles as well as corresponding thermal conductivity and dielectric properties is obtained. SEM observations show that the hybrid filler particles are agglomerated around the LDPE matrix particles, and within the agglomerates the smaller-sized nitride particles in the hybrid filler can easily form thermally conductive networks to make the composites with high thermal conductivity. At the same time, the increase of the value D_k of the composites is restricted due to the presence of HGMs.     

Nanocrystalline cobalt-oxide powders by solution-combustion synthesis and their application in chemical sensors

The present study demonstrates the relationship between the combustion reaction mechanism induced by the exothermicity of the cobalt nitrate-glycine solution-combustion reactions and morphological details of the nanocrystalline Co₃O₄. The thermal decomposition pathway and the amount of the heat liberated in combustion are defined by the exothermic reaction between gaseous NH₃ and N₂O species. A direct evidence that the exothermicity of the combustion reaction plays an important role in formation of the powders with different morphology was obtained from the scanning and transmission electron microscopies. In contrast to stoichiometric reaction, where the short-string Co₃O₄ particles form hard agglomerates, the energetically softer 50% fuel lean reaction is responsible for weak bonds between Co₃O₄ particles and formation of the loose cauliflower-like agglomerates. The latter powder with the specific surface area of 64.4 m²/g and the average crystallite size of ～11 nm was used for the processing of drop-coated sensors, which showed a superior sensor response toward 20 ppm of acetone in 25% r.h. humidity and at low operating temperature of 150 °C.     

Urea decomposition enhancing the hydrothermal synthesis of lithium iron phosphate powders: Effect of the lithium precursor

The synthesis of LiFePO₄ (hereafter referred as LFP) using urea as a reducing agent under hydrothermal conditions was investigated. The synthesis was carried out by varying the temperature (150–200 °C), at different times from 6 to 24 h, and using different precursors of Li ions (LiCl, LiNO₃, LiOH, and Li₂SO₄), to determine the effect of these parameters on the crystallization process of the reaction products. These were characterized by XRD, FT-IR, and FE-SEM. The results showed that the differences in the lattice parameters calculated by Rietveld refinement are affected by the synthesis temperature. In addition, the crystallization of single-phase LiFePO₄ powders was achieved by the urea decomposition that occurred at reaction times longer than 12 h and at moderate temperatures (170–180 °C). The crystallization of LFP particles was promoted by a dissolution-precipitation mechanism, but it was not conducted in a single step, because intermediate secondary phases were produced at reaction intervals below 6 h. A crystal growth stage involving the dissolution-crystallization of intermediate secondary phases led to the formation of large particle agglomerates of LiFePO₄ exhibiting a flower-like morphology when the synthesis was carried out using Li₂SO₄. When LiCl, LiOH, and LiNO₃ were used, large bulky agglomerates were obtained.     

Rapid hydrothermal synthesis of SrMo1−xWxO4 powders: Structure and luminescence characterization

Strontium molybdate, strontium tungstate particles and their solid solutions (SrMo_1?xW_xO₄) with 0 ? x ? 1.0, were synthesised by means of a hydrothermal process. Crystallisation of SrMo_1?xW_xO₄ particles took place rapidly using SrSO₄ as the Sr precursor under hydrothermal conditions involving stirring (130 rpm) at 150 or 200 °C for 2 h. Structural analyses of the powders were conducted by XRD with Rietveld refinement and FT-Raman spectroscopy, and the particle shape was observed by FE-SEM. Lattice parameter measurements indicated a linear dependence of both “a₀” and “c₀” in the scheelite structured SrMo_1?xW_xO₄ with a changing W content following Vegard’s law. These analyses also provided evidence of the structural variation localised in the tetrahedral site as a result of the simultaneous incorporation of MoO₄ and WO₄ in the solid solutions formed in the compositional range of 9 ? x ? 60 mol%. The SrMo_1?xW_xO₄ particles exhibited a predominantly euhedral shuttle-shaped morphology and particle sizes varying between 0.75 and 1.5 μm. The particle growth was affected by increasing the reaction temperature and the tungsten concentration. Photoluminescence analysis (PL) revealed a marked attenuation of the blue and green emissions preferentially for the powder containing 48.5 mol% of W, which makes it potentially useful for optoelectronic applications.     

Synthesis of γ-Al2O3 nanopowders by freeze-drying

This work studies the synthesis of γ-Al₂O₃ nanopowders by a freeze-drying method. Aqueous solutions of Al₂(SO₄)₃·18H₂O were used as precursors to Al concentrations of 0.76, 1.00 and 1.40 M. Homogeneous spherical granules with diameters ranging from 1 to 100 μm have been obtained. These porous granules are constituted by soft agglomerates of nanoparticles with primary particle size lower than 20 nm. The microstructure of the agglomerates largely depends on the freezing kinetics. After drying amorphous aluminium sulphate powder is obtained that decomposes at 825 °C leading to the formation of γ-Al₂O₃. Physicochemical study of the freeze-dried powders is performed through particle size distribution and zeta potential measurements. The characterisation of the powders is evaluated considering the influence of processing parameters such as the salt concentration, the freezing rate and the thermal treatment for the synthesis and the dispersing conditions of the obtained powders. By adjusting the dispersing conditions a minimum particle size <30 nm is measured, thus confirming that granules can be easily dispersed into nanoparticles.     

Microstructure characterization,mechanical properties,compressibility and sintering behavior of Al-B4C nanocomposite powders

In the present work, Al-xB₄C nanocomposite (x = 0, 1, 2, 3, 4 and 5 in wt%, having the average B₄C size of 50 nm) were prepared using a high-energy ball mill. The milling times up to 16 h were applied. Then, the microstructural evolutions, mechanical properties, compressibility and sintering behavior of nanocomposites were investigated. The changes in powders morphology and microstructure during the milling process were characterized by laser diffraction particle size analyzer (LDA), SEM, XRD, EDS and TEM techniques. Compressibility and sintering behavior of milled powders compacted under different pressures (100–900 MPa) and at different sintering temperatures (500, 550 and 600 °C) were also studied. The pressing behavior of the nanocomposites was analyzed using linear compaction equations developed by Heckel, Panelli-Filho and Ge. The results showed the significant effects of B₄C amounts and sintering temperatures on the compressibility and sintering behavior of nanocomposites. The increase in the B₄C amount led to a decrease in both the compressibility rate and the sinterability of specimens. The maximum compression strength of 265 MPa and Vickers hardness of 165 VHN were obtained for Al-5 wt.% B₄C nanocomposite milled for 16 h followed by sintering at 600 °C.     

A novel wet polymeric precipitation synthesis method for monophasic β-TCP

β-Tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP) powders were synthesized using wet polymeric precipitation method for the first time to our best knowledge. The results of X-ray diffraction analysis showed the formation of almost single a Ca-deficient hydroxyapatite (CDHA) phase of a poor crystallinity already at room temperature. With continuously increasing the calcination temperature up to 800 °C the crystalline β-TCP was obtained as the main phase. It was demonstrated that infrared spectroscopy is very effective method to characterize the formation of β-Ca₃(PO₄)₂. The SEM results showed that β-Ca₃(PO₄)₂ solids were homogeneous having a small particle size distribution. The β-TCP powders consisted of spherical particles varying in size from 100 to 300 nm. Fabricated β-TCP specimens were placed to the bones of the rats and maintained for 1–2 months. The histological properties of these samples will be also investigated.     

Measurement of particle size distribution of silica nanoparticles by interactive force apparatus under an electric field

This paper describes the measurement of particle size distribution of silica nanoparticles by interactive force apparatus (IFA) under an electric field in order to suggest the application of the apparatus to the measurement of particle size distribution. The results were compared with results obtained from size measurement by dynamic light scattering. D₅₀ measured by IFA was closer to the average particle size determined by TEM (5 nm). Also, when compared the results under three different supply voltage, (1) the results at 0.01 and 0.02 V were almost identical while (2) these results were different from the one at 0.04 V. The results indicate that breakage of coagulated particles possibly occur due to electric breakdown. The distribution measured by IFA (D₅₀ = 5–7 nm) was larger than the one measured by DLS (D₅₀ = 1 nm). The electric breakdown was explained by curve fitting of three different particle size distribution functions with particle size distribution obtained from IFA measurement.     

Synthesis of mesoporous CaCO3 particles by a spray drying method from the stable suspensions achieved in a beads mill

Dispersion of nanoparticles in liquids is an important issue on various applications. CaCO₃ agglomerates were disintegrated into its nanoparticles by a beads mill. The dynamic light scattering (DLS) method showed the size of dispersed particles of 22 nm reduced from the initial size of 130 nm. The effectiveness of smaller beads on the dispersion was explained by their enough impact energy and their high collision frequency. No further grinding of nanoparticles by the beads was explained by the short relaxation time of nanoparticles. The mesoporous CaCO₃ particles were synthesized from the stable suspensions by the spray drying method. As the dispersion air flowrate increased, the particle size decreased due to the smaller droplet size. Non-spherical particles were explained with the velocity difference between the colloidal solution and the dispersion air, with the longer momentum transfer time and with the faster evaporation rate. The pores originated from the spaces between the beads-milled particles, which was also created by the shear force.