A facile and effective strategy that can be used to fabricate electrically conductive membranes (ECMs) of diverse filtration performance (i.e., water productivity and solute rejection) is not available yet. Herein, we report a facile method that enables the fabrication of ECMs of a broad performance range. The method is based on the use of polyethylenimine (PEI), glutaraldehyde, and any of a diverse set of conductive materials to cast an electrically conductive layer atop any of a diverse set of substrates (i.e., from microfiltration to reverse osmosis membranes). We developed the reported ECM fabrication method using graphite as the conductive material and PVDF membranes as substrates. We demonstrate that graphite-PVDF ECMs were stable and electrically conductive and could be successfully used for solute filtration and electrochemical degradation. We also confirmed that the PEI/glutaraldehyde-based ECM fabrication method is suitable for conductive materials other than graphite, including carbon nanotubes, reduced graphene oxide, activated charcoal, and silver nanoparticles. Compared with the substrates used for their fabrication, ECMs showed low electrical sheet resistances that varied with conductive material, increased solute rejection, and reduced water permeance. Taken together, this work presents a promising general strategy for the fabrication of ECMs for environmental applications from diverse substrates and conductive materials.
Thin-film nanocomposite (TFN) membranes are emerging water-purification membranes that could provide enhanced water permeance with similar solute removal over traditional thin-film composite (TFC) membranes. However, the effects of nanofiller incorporation on active layer physico-chemical properties have not been comprehensively studied. Accordingly, we aimed to understand the correlation between nanofillers, active layer physico-chemical properties, and membrane performance by investigating whether observed performance differences between TFN and control TFC membranes correlated with observed differences in physico-chemical properties. The effects of nanofiller loading, surface area, and size on membrane performance, along with active layer physico-chemical properties, were characterized in TFN membranes incorporated with Linde Type A (LTA) zeolite and zeolitic imidazole framework-8 (ZIF-8). Results show that nanofiller incorporation up to ~0.15 wt% resulted in higher water permeance and unchanged salt rejection, above which salt rejection decreased 0.9-25.6% and 26.1-48.3% for LTA-TFN and ZIF-8-TFN membranes, respectively. Observed changes in active layer physico-chemical properties were generally unsubstantial and did not explain observed changes in TFN membrane performance. Therefore, increased water permeance in TFN membranes could be due to preferential water transport through porous structures of nanofillers or along polymer-nanofiller interfaces. These findings offer new insights into the development of high-performance TFN membranes for water/ion separations.
Two aromatic polyamidesâpoly(3,3'-dihydroxybenzidine terephthalamide) (DHTA) and poly(3,3'-dihydroxybenzidine isophthalamide) (DHIA)âare compared for their ability to remove salts from water. DHTA is linear and rigid whereas DHIA is nonlinear and semirigid. DHTA and DHIA were selected as they allow us to investigate the effect of polymer backbone geometry on salt exclusion in a non-crosslinked thin film membrane, independently of the backbone chemistry. Because of their differences in solution viscosity, spin coating parameters for DHTA and DHIA solutions were optimized separately to produce thin film composites (TFCs) with reproducible membrane properties. The resulting DHTA TFCs displayed salt rejections of 87.8% (NaCl), 97.0% (MgSO4), and 80.3% (CaCl2). In comparison, DHIA TFCs demonstrated poor salt rejections of 21.0% (NaCl), 29.3% (MgSO4), and 15.4% (CaCl2). Cross-sectional SEM images of DHTA and DHIA films reveal that DHTA has a stratified (layered) morphology whereas DHIA exhibits a dense, featureless morphology. Both DHTA and DHIA TFCs exhibit similar surface morphology, contact angle, surface charge, and water uptake. PEG rejection experiments indicate that the average pore size of DHTA TFCs is â¼2 nm while DHIA TFCs have an average pore size of â¼3 nm. Our findings illustrate that using a rigid, linear aromatic polyamide gives an active layer with a stratified morphology, uniplanar orientation, smaller pores, and higher salt rejection, whereas the nonlinear aromatic polyamide analogue results in an isotropic active layer with larger pores and lower salt rejection.
Membrane distillation (MD) has been touted as a promising technology for niche applications such as desalination of surfactant- and oil-containing feed streams. Hitherto, the deployment of conventional hydrophobic MD membranes for such applications is limited and unsatisfactory. This is because the presence of surfactants and oils in aqueous feed streams reduces the surface-tension of these media significantly and the attachment of these contaminants onto hydrophobic membrane surfaces often leads to membrane fouling and pore wetting, which compromises on the quantity and quality of water recovered. Endowing MD membranes with surfaces of special wettabilities has been proposed as a strategy to combat membrane fouling and pore wetting. This involves the design of local kinetic energy barriers such as multilevel re-entrant surface structures, surfaces with ultralow surface-energies, and interfacial hydration layers to impede transition to the fully-wetted Wenzel state. This review critiques the state-of-the-art fabrication and surface-modification methods as well as practices used in the development of omniphobic and Janus MD membranes with specific emphasis on the advances, challenges, and future improvements for application in challenging surfactant- and oil-containing feed streams.
Commercial hydrophobic poly(vinylidene fluoride) (PVDF) membranes are vulnerable to membrane fouling and pore wetting, hampering the use of membrane distillation (MD) for the treatment of surfactant- and oil-containing feed streams. To address these challenges, we designed novel Janus membranes with multilevel roughness to mitigate foulant adhesion and prevent pore wetting. Specifically, fouling- and wetting-resistant Janus MD membranes with hierarchically structured surfaces were tailored via a facile technique that involved oxidant-induced dopamine polymerization followed by in situ immobilization of silver nanoparticles (AgNPs) on commercial PVDF hollow fiber substrates. These membranes demonstrated outstanding antifouling properties and salt rejection performances in comparison to membranes with single-level structures. We ascribed the membranes' excellent performances to the coupled effects of improved surface hydrophilicity and self-healing mechanism brought about by AgNPs. Furthermore, the newly engineered membranes exhibited antibacterial properties in Bacillus acidicola solutions as evidenced by clear inhibition zones observed on a confocal laser scanning microscope. The development of hierarchically structured Janus MD membranes with multilevel roughness paves a way to mitigate membrane fouling and pore wetting caused by low-surface-tension feed streams in the MD process.
