RESUMO
In the past 30 years, plasma polymerization has emerged as a versatile technique for depositing ultrathin nanocoating on a variety of substrates for applications that range from providing lubricity to the substrate, protection from harsh environments, promoting adhesion, surface modification to applications of coating in ultrafiltration and gas separation membranes. Applications in the field of volatile organic compound (VOC) recovery and membrane distillation have also gained importance in recent years. Most of these applications use silicone and fluorosilicone-based plasma polymers that provide versatility, good separation characteristics, and long-term stability to the membrane. However, plasma polymers are known to age with time. The current study focuses on the aging behavior of silicone and fluorosilicone plasma polymers in different environments that include air, ionized air, heat, aqueous solutions of inorganic chemicals, as well as harsh solvents such as hexane, dichloromethane (DCM), and toluene. Membrane gas permeance and gas selectivity were used to quantitatively measure the aging behavior of the coatings on gas separation membranes, while water and VOC flux were used to measure the effect of aging for membranes designed for membrane distillation and VOC separation. It was found that while all plasma polymers of this study showed changes in membrane gas permeance on exposure to air, they fundamentally retained their membrane separation characteristics in all the studied environments. Significant changes in gas permeability characteristics were observed on exposure of the membranes to organic solvents like dichloromethane, 2-propanol, hexane, and toluene, which are attributed to dimensional changes in the hollow fiber substrate rather than changes in plasma polymer characteristics. Ionized air was also found to have a significant effect on the gas permeability characteristic of the membranes, reducing the gas permeance by as much as 50% in some cases. This is attributed to accelerated oxidation and crosslinking of the polymer in ionized air. XPS studies showed an increase in the oxygen content of the polymer on aging. Differences were found in the aging behavior of polymer coatings made from different monomers with long-chain monomers such as hexamethyltrisiloxane offering more stable coatings. The cross-link density of the polymer also influenced the aging behavior, with the more cross-linked polymer showing a lesser influence on aging in a chemical environment. No significant effect of aging was found on applications of these polymer coatings in the field of membrane distillation, pervaporation, and VOC removal, and a stable performance was observed over a long period of time. It was also noted that the selection of co-monomers played a significant role in membrane distillation, with polymers forming fluoro co-monomers giving better results. The current study also demonstrated the usefulness of plasma polymers in controlling the pore size of microporous membranes that can find useful applications in bio-filtration and VOC recovery.
RESUMO
High water vapor flux at low brine temperatures without surface fouling is needed in membrane distillation-based desalination. Brine crossflow over surface-modified hydrophobic hollow fiber membranes (HFMs) yielded fouling-free operation with supersaturated solutions of scaling salts and their precipitates. Surface modification involved an ultrathin porous polyfluorosiloxane or polysiloxane coating deposited on the outside of porous polypropylene (PP) HFMs by plasma polymerization. The outside of hydrophilic MicroPES HFMs of polyethersulfone was also coated by an ultrathin coating of porous plasma-polymerized polyfluorosiloxane or polysiloxane rendering the surface hydrophobic. Direct contact membrane distillation-based desalination performances of these HFMs were determined and compared with porous PP-based HFMs. Salt concentrations of 1, 10, and 20 wt% were used. Leak rates were determined at low pressures. Surface and cross-sections of two kinds of coated HFMs were investigated by scanning electron microscopy. The HFMs based on water-wetted MicroPES substrate offered a very thin gas gap in the hydrophobic surface coating yielding a high flux of 26.4-27.6 kg/m2-h with 1 wt% feed brine at 70 °C. The fluxes of HFMs on porous PP substrates having a long vapor diffusion path were significantly lower. Coated HFM performances have been compared with flat hydrophilic membranes of polyvinylidene fluoride having a similar plasma-polymerized hydrophobic polyfluorosiloxane coating.
