Plasma Polymerized Coatings on Hollow Fiber Membranes-Applications and Their Aging Characteristics in Different Media

Abstract

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.