We examine effects of hydrodynamics on phase separation morphologies developed during drying of thin films containing a volatile solvent and two dissolved polymers. Cahn-Hilliard and Flory-Huggins theories are used to describe the free energy of the phase separating systems. The thin films, considered as Newtonian fluids, flow in response to Korteweg stresses arising due to concentration non-uniformities that develop during solvent evaporation. Numerical simulations are employed to investigate the effects of a Peclet number, defined in terms of system physical properties, as well as the effects of parameters characterizing the speed of evaporation and preferential wetting of the solutes at the gas interface. For systems exhibiting preferential wetting, diffusion alone is known to favor lamellar configurations for the separated phases in the dried film. However, a mechanism of hydrodynamic instability of a short length scale is revealed, which beyond a threshold Peclet number may deform and break the lamellae. The critical Peclet number tends to decrease as the evaporation rate increases and to increase with the tendency of the polymers to selectively wet the gas interface. As the Peclet number increases, the instability moves closer to the gas interface and induces the formation of a lateral segregation template that guides the subsequent evolution of the phase separation process. On the other hand, for systems with no preferential wetting or any other property asymmetries between the two polymers, diffusion alone favors the formation of laterally separated configurations. In this case, concentration perturbation modes that lead to enhanced Korteweg stresses may be favored for sufficiently large Peclet numbers. For such modes, a second mechanism is revealed, which is similar to the solutocapillary Marangoni instability observed in evaporating solutions when interfacial tension increases with the concentration of the non-volatile component. This mechanism may lead to multiple length scales in the laterally phase separated configurations.
A membrane ozonation contactor was built to investigate ozonation using tubular membranes and inform computational fluid dynamics (CFD) studies. Non-porous tubular polydimethylsiloxane (PDMS) membranes of 1.0–3.2 mm inner diameter were tested at ozone gas concentrations of 110–200 g/m3 and liquid side velocities of 0.002–0.226 m/s. The dissolved ozone concentration could be adjusted to up to 14 mg O3/L and increased with decreasing membrane diameter and liquid side velocity. Experimental mass transfer coefficients and molar fluxes of ozone were 2.4 × 10−6 m/s and 1.1 × 10−5 mol/(m2 s), respectively, for the smallest membrane. CFD modelling could predict the final ozone concentrations but slightly overestimated mass transfer coefficients and molar fluxes of ozone. Model contaminant degradation experiments and UV light absorption measurements of ozonated water samples in both ozone (O3) and peroxone (H2O2/O3) reaction systems in pure water, river water, wastewater effluent, and solutions containing humic acid show that the contactor system can be used to generate information on the reactivity of ozone with different water matrices. Combining simple membrane contactors with CFD allows for prediction of ozonation performance under a variety of conditions, leading to improved bubble-less ozone systems for water treatment.
The ozonation of 90 chemically diverse organic micropollutants (OMPs) including four classes of illicit drugs and their metabolites was studied in pure buffered water, tap water and wastewater effluent at three specific ozone doses and three pH levels.
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