An official website of the United States government
Abstract Materials combining an asymmetric pore structure with mesopores everywhere enable high surface area accessibility and fast transport, making them attractive for e.g., energy conversion and storage applications. Block copolymer (BCP)/inorganic precursor co‐assembly combined with non‐solvent induced phase separation (NIPS) provides a route to materials in which a mesoporous top surface layer merges into an asymmetric support with graded porosity along the film normal and mesopores throughout. Here, the co‐assembly and non‐solvent‐induced phase separation (CNIPS) of poly(isoprene)‐b‐poly(styrene)‐b‐poly(4‐vinylpyridine) (ISV) triblock terpolymer and titanium dioxide (TiO2) sol‐gel nanoparticlesare reported. Heat‐treatment in air results in free‐standing asymmetric porous TiO2. Further thermal processing in ammonia results in free‐standing asymmetric porous titanium nitride (TiN). processing changes alter structural membrane characteristics is demonstrated. Changing the CNIPS evaporation time results in various membrane cross‐sections ( finger‐like to sponge‐like). Oxide and nitride material composition, crystallinity, and porosity are tuned by varying thermal processing conditions. Finally, thermal processing condition effects are probed on phase‐pure asymmetric nitride membrane behavior using cyclic voltammetry to elucidate their influence, e.g., on specific capacitance. Results provide further insights into improving asymmetric and porous materials for applications including energy conversion and storage, separation, and catalysis and motivate a further expansion of CNIPS to other (in)organic materials.
more »
« less
Non-Equilibrium Block Copolymer Self-Assembly Based Porous Membrane Formation Processes Employing Multicomponent Systems
Porous polymer-derived membranes are useful for applications ranging from filtration and separation technologies to energy storage and conversion. Combining block copolymer (BCP) self-assembly with the industrially scalable, non-equilibrium phase inversion technique (SNIPS) yields membranes comprising periodically ordered top surface structures supported by asymmetric, hierarchical substructures that together overcome performance tradeoffs typically faced by materials derived from equilibrium approaches. This review first reports on recent advances in understanding the top surface structural evolution of a model SNIPS-derived system during standard membrane formation. Subsequently, the application of SNIPS to multicomponent systems is described, enabling pore size modulation, chemical modification, and transformation to non-polymeric materials classes without compromising the structural features that define SNIPS membranes. Perspectives on future directions of both single-component and multicomponent membrane materials are provided. This points to a rich and fertile ground for the study of fundamental as well as applied problems using non-equilibrium-derived asymmetric porous materials with tunable chemistry, composition, and structure.
more »
« less
- PAR ID:
- 10450347
- Date Published:
- Journal Name:
- Polymers
- Volume:
- 15
- Issue:
- 9
- ISSN:
- 2073-4360
- Page Range / eLocation ID:
- 2020
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Block copolymer self-assembly in conjunction with nonsolvent-induced phase separation (SNIPS) has been increasingly leveraged to fabricate integral-asymmetric membranes. The large number of formulation and processing parameters associated with SNIPS, however, has prevented the reliable construction of high performance membranes. In this study, we apply dynamical self-consistent field theory to model the SNIPS process and investigate the effect of various parameters on the membrane morphology: solvent selectivity, nonsolvent selectivity, initial film composition, and glass transition composition. We examine how solvent selectivity and concentration of polymers in the film impact the structure of micelles that connect to form the membrane matrix. In particular, we find that preserving the order in the surface layer and forming a connection between the supporting and surface layer are nontrivial and sensitive to each parameter studied. The effect of each parameter is discussed, and suggestions are made for successfully fabricating viable block copolymer membranes.more » « less
-
null (Ed.)Initiated chemical vapor deposition (iCVD) was used to coat two porous substrates (i.e., hydrophilic cellulose acetate (CA) and hydrophobic polytetrafluoroethylene (PTFE)) with a crosslinked fluoropolymer to improve membrane wetting resistance. The coated CA membrane was superhydrophobic and symmetric. The coated PTFE membrane was hydrophobic and asymmetric, with smaller pore size and lower porosity on the top surface than on the bottom surface. Membrane performance was tested in membrane distillation experiments with (1) a high-salinity feed solution and (2) a surfactant-containing feed solution. In both cases, the coated membranes had higher wetting resistance than the uncoated membranes. Notably, wetting resistances were better predicted by LEP distributions than by minimum LEP values. When LEP distributions were skewed towards high LEP values (i.e., when small pores with high LEP were greater in number), significant (measurable) salt passage did not occur. For the high-salinity feed solution, the coated PTFE membrane had greater wetting resistance than the coated CA membrane; thus, reduced surface pore size/porosity (which may reduce intrapore scaling) was more effective than increased surface hydrophobicity (which may reduce surface nucleation) in preventing scaling-induced wetting. Reduced pore size/porosity was equally as effective as increased hydrophobicity in resisting surfactant-induced wetting. However, reduced porosity can negatively impact water flux; this represents a permeability/wetting resistance tradeoff in membrane distillation – especially for high-salinity applications. Membrane and/or membrane coating properties must be optimized to overcome this permeability/wetting resistance tradeoff and make MD viable for the treatment of challenging streams. Then, increasing hydrophobicity may not be necessary to impart high wetting resistance to porous membranes. These results are important for future membrane design, especially as manufacturers seek to replace perfluorinated materials with environmentally friendly alternatives.more » « less
-
Abstract Surface segregation in blended polymer films has attracted much interest in fundamental research as well as for practical applications. A variety of methodologies have been proposed for controlling surface segregation. They often require long annealing times, however, to achieve thermodynamic equilibrium. Here, a strategy and proof‐of‐principle experiments are described to control surface segregation of thin block‐copolymer (BCP) layers on top of a homopolymer in a single casting step from blended BCP/homopolymer solutions. The surface coverage by the minor constituent BCP (2–10 wt%) is accomplished despite almost identical surface energies of BCP and homopolymer constituents. Immersing this casted solution into water for nonsolvent induced phase separation (NIPS), a nonequilibrium process, affords solidified bilayer ultrafiltration membranes composed of a thin porous surface layer of self‐assembled BCP atop an asymmetric porous homopolymer substructure. Key to successful BCP surface segregation is the choice of a binary solvent system based on careful considerations of solvent surface energies and polymer‐solvent interaction parameters. Furthermore, stabilizing the BCP micellar structure by a divalent metal additive is also essential. The approach provides a cost‐effective method for fabricating bilayer‐type asymmetric ultrafiltration membranes with uniform BCP self‐assembly based selective top surface pore layers in a single casting step.more » « less
-
With drinking water regulations forthcoming for per- and polyfluoroalkyl substances (PFAS), the need for cost-effective treatment technologies has become urgent. Adsorption is a key process for removing or concentrating PFAS from water; however, conventional adsorbents operated in packed beds suffer from mass transfer limitations. The objective of this study was to assess the mass transfer performance of a porous polyamide adsorptive membrane for removing PFAS from drinking water under varying conditions. We conducted batch equilibrium and dynamic adsorption experiments for perfluorooctanesulfonic acid, perfluorooctanoic acid, perfluorobutanesulfonic acid, and undecafluoro-2-methyl-3-oxahexanoic acid (i.e., GenX). We assessed various operating and water quality parameters, including flow rate (pore velocity), pH, ionic strength (IS), and presence of dissolved organic carbon. Outcomes revealed that the porous adsorptive membrane was a mass transfer-efficient platform capable of achieving dynamic capacities similar to equilibrium capacities at fast interstitial velocities. The adsorption mechanism of PFAS to the membrane was a mixture of electrostatic and hydrophobic interactions, with pH and IS controlling which interaction was dominant. The adsorption capacity of the membrane was limited by its surface area, but its site density was approximately five times higher than that of granular activated carbon. With advances in molecular engineering to increase the capacity, porous adsorptive membranes are well suited as alternative adsorbent platforms for removing PFAS from drinking water.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/polym15092020
