Applications of Aerosol Technologies in the Silicon Industry

In this dissertation, the focus was on two unit operations that have the potential to significantly lower the cost and energy required for refining silicon. First, the removal of carbon from silicon kerf (sawing dust from wafering) was examined to enable its recycling. Second, silane pyrolysis was studied to better understand the dynamics of the initial stages of silicon aerosol formation and growth

Gas-to-nanotextile: high-performance materials from floating 1D nanoparticles

Suspended in the gas phase, 1D inorganic nanoparticles (nanotubes and nanowires) grow to hundreds of microns in a second and can be thus directly assembled into freestanding network materials. The corresponding process continuously transforms gas precursors into aerosols into aerogels into macroscopic nanotextiles. By enabling the assembly of very high aspect ratio nanoparticles, this processing route has translated into high-performance structural materials, transparent conductors and battery anodes, amongst other embodiments. This paper reviews progress in the application of such manufacturing process to nanotubes and nanowires. It analyses 1D nanoparticle growth through floating catalyst chemical vapour deposition (FCCVD), in terms of reaction selectivity, scalability and its inherently ultra-fast growth rates (107-108 atoms per second) up to 1000 times faster than for substrate CVD. We summarise emerging descriptions of the formation of aerogels through percolation theory and multi-scale models for the collision and aggregation of 1D nanoparticles. The paper shows that macroscopic ensembles of 1D nanoparticles resemble textiles in their porous network structure, high flexibility and damage-tolerance. Their bulk properties depend strongly on inter-particle properties and are dominated by alignment and volume fraction. Selected examples of nanotextiles that surpass granular and monolithic materials include structural fibres with polymer-like toughness, transparent conductors, and slurry-free composite electrodes for energy storage.Comment: 36 pages, 25 figure

The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source

Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O-3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O-3 -> IOIO4 and (R2) IOIO4 + H2O -> HIO3 + HOI + O-(1)(2). The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.Peer reviewe

Enhanced growth rate of atmospheric particles from sulfuric acid

In the present-day atmosphere, sulfuric acid is the most important vapour for aerosol particle formation and initial growth. However, the growth rates of nanoparticles (<10 nm) from sulfuric acid remain poorly measured. Therefore, the effect of stabilizing bases, the contribution of ions and the impact of attractive forces on molecular collisions are under debate. Here, we present precise growth rate measurements of uncharged sulfuric acid particles from 1.8 to 10 nm, performed under atmospheric conditions in the CERN (European Organization for Nuclear Research) CLOUD chamber. Our results show that the evaporation of sulfuric acid particles above 2 nm is negligible, and growth proceeds kinetically even at low ammonia concentrations. The experimental growth rates exceed the hard-sphere kinetic limit for the condensation of sulfuric acid. We demonstrate that this results from van der Waals forces between the vapour molecules and particles and disentangle it from charge–dipole interactions. The magnitude of the enhancement depends on the assumed particle hydration and collision kinetics but is increasingly important at smaller sizes, resulting in a steep rise in the observed growth rates with decreasing size. Including the experimental results in a global model, we find that the enhanced growth rate of sulfuric acid particles increases the predicted particle number concentrations in the upper free troposphere by more than 50 %

Enhanced growth rate of atmospheric particles from sulfuric acid

In the present-day atmosphere, sulfuric acid is the most important vapour for aerosol particle formation and initial growth. However, the growth rates of nanoparticles (<10 nm) from sulfuric acid remain poorly measured. Therefore, the effect of stabilizing bases, the contribution of ions and the impact of attractive forces on molecular collisions are under debate. Here, we present precise growth rate measurements of uncharged sulfuric acid particles from 1.8 to 10 nm, performed under atmospheric conditions in the CERN (European Organization for Nuclear Research) CLOUD chamber. Our results show that the evaporation of sulfuric acid particles above 2 nm is negligible, and growth proceeds kinetically even at low ammonia concentrations. The experimental growth rates exceed the hard-sphere kinetic limit for the condensation of sulfuric acid. We demonstrate that this results from van derWaals forces between the vapour molecules and particles and disentangle it from charge-dipole interactions. The magnitude of the enhancement depends on the assumed particle hydration and collision kinetics but is increasingly important at smaller sizes, resulting in a steep rise in the observed growth rates with decreasing size. Including the experimental results in a global model, we find that the enhanced growth rate of sulfuric acid particles increases the predicted particle number concentrations in the upper free troposphere by more than 50 %.Peer reviewe

Molecular understanding of the suppression of new-particle formation by isoprene

Nucleation of atmospheric vapours produces more than half of global cloud condensation nuclei and so has an important influence on climate. Recent studies show that monoterpene (C10H16) oxidation yields highly oxygenated products that can nucleate with or without sulfuric acid. Monoterpenes are emitted mainly by trees, frequently together with isoprene (C5H8), which has the highest global emission of all organic vapours. Previous studies have shown that isoprene suppresses new-particle formation from monoterpenes, but the cause of this suppression is under debate. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we show that isoprene reduces the yield of highly oxygenated dimers with 19 or 20 carbon atoms - which drive particle nucleation and early growth - while increasing the production of dimers with 14 or 15 carbon atoms. The dimers (termed C-20 and C-15, respectively) are produced by termination reactions between pairs of peroxy radicals (RO2 center dot) arising from monoterpenes or isoprene. Compared with pure monoterpene conditions, isoprene reduces nucleation rates at 1.7 nm (depending on the isoprene = monoterpene ratio) and approximately halves particle growth rates between 1.3 and 3.2 nm. However, above 3.2 nm, C-15 dimers contribute to secondary organic aerosol, and the growth rates are unaffected by isoprene. We further show that increased hydroxyl radical (OH center dot) reduces particle formation in our chemical system rather than enhances it as previously proposed, since it increases isoprene-derived RO2 center dot radicals that reduce C-20 formation. RO2 center dot termination emerges as the critical step that determines the highly oxygenated organic molecule (HOM) distribution and the corresponding nucleation capability. Species that reduce the C-20 yield, such as NO, HO2 and as we show isoprene, can thus effectively reduce biogenic nucleation and early growth. Therefore the formation rate of organic aerosol in a particular region of the atmosphere under study will vary according to the precise ambient conditions.Peer reviewe

Role of iodine oxoacids in atmospheric aerosol nucleation

Iodic acid (HIO₃) is known to form aerosol particles in coastal marine regions, but predicted nucleation and growth rates are lacking. Using the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber, we find that the nucleation rates of HIO₃ particles are rapid, even exceeding sulfuric acid–ammonia rates under similar conditions. We also find that ion-induced nucleation involves IO₃⁻ and the sequential addition of HIO₃ and that it proceeds at the kinetic limit below +10°C. In contrast, neutral nucleation involves the repeated sequential addition of iodous acid (HIO₂) followed by HIO₃, showing that HIO₂ plays a key stabilizing role. Freshly formed particles are composed almost entirely of HIO₃, which drives rapid particle growth at the kinetic limit. Our measurements indicate that iodine oxoacid particle formation can compete with sulfuric acid in pristine regions of the atmosphere