Studies on nanobubbles in aqueous solutions

摘要

In this thesis, the nanobubbles in the aqueous solutions have been studied by using combination of static and dynamic laser light scattering (LLS), isothermal compressibility measurements and Zeta-potential measurements. We found that the nanobubbles extensively exist in aqueous solutions and the interface of each nanobubble is negatively charged. The addition of electrolytes can destabilize such interface to induce the coalescence of nanobubbles.;Chapter 1 briefly introduces the background, problems, applications as well as recent progress of the nanobubbles research. The relationship between the formation/stabilization of nanobubbles and the long-rang structures of water molecules, particularly the restructuring of water molecules at the water/gas interface, are emphasized.;Chapter 2 introduces the theories of static and dynamic light scattering and Zeta-potential measurements as well as the details of the instrument set-up. In this chapter, the fundamental equations of the scattering theory are figured out basis on the quasi-classical electrodynamics and combination of the statistical mechanics as well as molecular dynamic theory. Finally, the statistical properties of photon counting are discussed.;In chapter 3, aqueous solutions of tetrahydrofuran, ethanol, urea and alpha-cyclodextrin were studied by a combination of static and dynamic laser light scattering (LLS). In textbooks, these small organic molecules are soluble in water so that there should be no observable large structures or density fluctuation in either static or dynamic LLS. However, a slow mode has been consistently observed in these aqueous solutions in dynamic LLS. Such a slow mode was previously attributed to some large complexes or supramolecular structures formed between water and these small organic molecules, Our current study reveals that it is actually due to the existence of small bubbles (∼100 nm in diameter) formed inside these solutions. Our direct evidence comes from the fact that it can be removed by repeated filtration and regenerated by air purging. Our results also indicate that the formation of such nanobubbles in small organic molecules aqueous solutions is a universal phenomenon. Such formed nanobubbles are rather stable. The measurement of isothermal compressibility confirms the existence of a low density micro-phase, presumably nanobubbles, in these aqueous solutions. Using a proposed structural model, i.e., each bubble is stabilized by small organic molecules adsorbed at the gas/water interface, we have, for the first time, estimated the pressure inside these nanobubbles.;In chapter 4, by using a combination of laser light scattering (LLS) and zeta-potential measurements, we investigated effects of salt concentration and pH on stability of the nanobubbles in alpha-cyclodextrin (alpha-CD) aqueous solutions. Our LLS results reveal that the nanobubbles are unstable in solutions with a higher ionic strength, just like colloidal particles in an aqueous dispersion, but become more stable in alkaline solutions. The zeta-potential measurement shows that the nanobubbles are negatively charged with an electric double layer, presumably due to the adsorption of negative OTT ions at the gas/water interface. It is this double layer that plays dual roles in the formation of stable nanobubbles in aqueous solutions of water-soluble organic molecules; namely, it not only provides a repulsive force to prevent the inter-bubble aggregation and coalescence, but also reduces the surface tension at the gas/water interface to decreases the internal pressure inside each bubble.;In chapter 5, the addition of salt can induce slow coalescence of nanobubbles (∼100 nm) in an aqueous solution of alpha-cyclodextrin (alpha-CD). A combination of static and dynamic laser light scattering was used to follow the coalescence. Our results reveal that its kinetic and structural properties follow some scaling laws; namely, the average size () of nanobubbles is related to their average mass () and the coalescence time (t) as dr and ∼ tgamma with two salt-concentration dependent scaling exponents (df and gamma) For a lower sodium chloride concentration (C NaCl = 40 mM), gamma = 0.13 +/- 0.01 and df = 1.71 +/- 0.02. The increase of CNaCl to 80 mM results in gamma = 0.32 +/- 0.01 and df = 1.99 +/- 0.01. The whole process has two main stages: the aggregation and the coalescence. At the lower C NaCl, the process essentially stops in the aggregation stage with some limited coalescence. At higher CNaCl leads the coalescence after the aggregation and results in large bubbles.