Peculiarities of Nanoparticle Formation and Implications to Generation of Environmental Aerosols
MetadataShow full item record
This Thesis considers peculiarities of nanoparticle formation from the gas in different systems. The main role of the surface condensation in the nanoparticle growth in metal flames was established through a series of experiments and was described by the developed model. The stagnation of the post-nucleation nanoparticle growth was experimentally revealed and theoretically explained. The influence of generation conditions on the post-processing nanoparticle properties was examined. The non-isothermal approach to correct the homogeneous nucleation theory was developed. The results of this work can be summarized in 3 categories: (1) Nanoparticle formation in metal flames. In this work, it was demonstrated that the surface condensation is a main process responsible for nanooxides growth during metal combustion. It was shown that the rate of this condensation growth is consistent with the exponential law, which could lead to the formation of the lognormal particle size distribution in the system, where the Brownian coagulation is suppressed. The post-nucleation stagnation of the nanoparticle growth was found. The particle overheating was suggested as a cause of the growth stagnation. The found stagnation leads to the accumulation of the supercritical clusters in the system generating nanoparticles. The role of these supercritical clusters in the nanoparticle agglomeration was considered. (2) Study of properties of nanoparticles generated in different metal flames. The light absorption, photoluminescence and magnetic properties of nanoparticles produced in different metal flames were examined. The significant broadening of the absorption edge was found in nanooxides produced by direct metal combustion. This broadening allowed one to excite the unforeseen photoluminescence from these nanoparticles. The significant light absorption in the visible light found in the titania particles produced by metal combustion allows one to consider these particles as a prospective photocatalyst. The unusual optical properties revealed were related to the extreme conditions of the nanoparticle formation, namely, to high energy release (about 5 eV per condensing molecule). The stabilization of spinel structure was found in iron oxide particles synthesized by iron combustion. It allowed one to produce nanoparticles with magnetization close to the high-limit value of the bulk. (3) Approach to correct the homogeneous nucleation theory. The existing homogeneous nucleation theory implies that nucleation occurs at isothermal conditions, i.e. subcritical clusters have the same temperature as the ambient gas does. However, the theory overestimates the actual nucleation rate and underestimates the critical cluster size. It is understandable that due to release of the latent heat of condensation, the cluster temperature in the nucleating system should be higher than the environment temperature. In this work, it was suggested the method to account for the cluster overheating during nucleation. It was demonstrated that the consistent description of the detailed balance in the nucleating system may allow one to evaluate magnitudes of overestimation of the actual nucleation rate and underestimation of the number of molecules in the critical cluster, usually obtained by the isothermal nucleation theory. The numerical estimates are in good agreement with the wellknown experimental results. The implications of the results to generation of atmospheric aerosols were discussed.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Environmental Engineering
Item Access Status
homogeneous nucleation theory