Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

Marques, Debora Salomon; Dorin, Rachel M.; Wiesner, Ulrich; Smilgies, Detlef‐M.; Behzad, Ali Reza; Vainio, Ulla; Peinemann, Klaus‐Viktor; Nunes, Suzana Pereira

doi:10.1016/j.polymer.2013.11.010

Cited by 51 publications

(75 citation statements)

References 19 publications

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“…As discussed by Krausch et al 65,67 for block copolymers in the melt, perforated lamellae could be favored if order is present in the bulk and none of the blocks has a strong preferential tendency to wet the surface. They could have a role in the formation of the commonly observed periodic morphology on the flat block copolymer membrane surface 113 . Other forms of complex periodic surface morphology have been predicted for 3D confinements 50,76 .…”

Section: Snips Processmentioning

confidence: 97%

“…While the ordered layer discussed above is mainly formed by selfassembly in the bulk, the surface pore morphology (< 100 nm) is probably affected by additional air (vapor)-solution interface effects. Time-resolved experiments indicated that the pores might start to be formed on the membrane surface even before the immersion in water, in the case of block copolymer SNIPS process 113 . We froze the membrane in liquid nitrogen after different casting/evaporation times and imaged them by cryo scanning electron microscopy.…”

Section: Snips Processmentioning

confidence: 99%

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Block Copolymer Membranes for Aqueous Solution Applications

2016

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Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.3

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Section: Snips Processmentioning

confidence: 97%

Section: Snips Processmentioning

confidence: 99%

Block Copolymer Membranes for Aqueous Solution Applications

2016

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“…This result is consistent with our previous findings for PS--b--P4VP copolymer. 42 At semi--dilute concentrations, micellar entities are close to each other, and, therefore, the SAXS measurement reflects the inter--micellar distances in the solution bulk. The GISAXS measurement, on the other hand, characterizes more surface effects and the first bulk sub--layers.…”

Section: Time--resolved Pore Formation Experimentsmentioning

confidence: 99%

Design of block copolymer membranes using segregation strength trend lines

Sutisna

Polymeropoulos

Musteata

et al. 2016

Mol. Syst. Des. Eng.

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CitationDesign of block copolymer membranes using segregation strength trend lines 2016 Mol. Syst. Des. Eng. Block copolymer self--assembly and non--solvent induced phase separation are now being combined to fabricate membranes with narrow pore size distribution, and high porosity. The method has the potential to be used with a broad range of tailor made block copolymers to control functionality and selectivity for specific separations. However, the extension of this process to any new copolymer is challenging and time consuming, due to the complex interplay of influencing parameters, such as solvent composition, polymer molecular weights, casting solution concentration, and evaporation time. We propose here an effective method for designing new block copolymer membranes. The method consists of predetermining a trend line for preparation of isoporous membranes, obtained by computing solvent properties, interactions and copolymer block sizes for a set of successful systems and using it as a guide to select the preparation conditions for new membranes. We applied the method to membranes based on poly(styrene--b--ethylene oxide) diblocks and extended it to newly synthesized poly(styrene--b--2--vinyl pyridine--b--ethylene oxide) (PS--b--P2VP--b--PEO) terpolymers. The trend line method can be generally applied to other new systems and is expected to dramatically shorten the path of isoporous membrane manufacture. The PS--b--P2VP--b--PEO membrane formation was investigated by in situ Grazing Incident Small Angle X--ray Scattering (GISAXS), which revealed a hexagonal micelle order with domains spacing clearly correlated to the membrane interpore distances. Eprint version

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“…Time-resolved cryo-TEM, small angle neutron scattering (SANS), [66][67][68][69] and SAXS data have recently been utilized to examine the dynamic evolution of the self-assembled nanostructure within the active layer during the solvent evaporation step of the SNIPS protocol (Fig. 4).…”

Section: Introductionmentioning

confidence: 99%

“…As solvent evaporates, the surface nanostructure undergoes a transition from a disordered morphology in the semidilute regime into various ordered states as a function of the polymer concentration. 67,68,70,71 For example, in a study with polyisoprene-b-polystyrene-b-poly(4-vinylpyridine) (PI-PS-P4VP) membranes, the block polymer in the cast film experienced a transformation from a body-centered cubic lattice into a simple cubic as the evaporation process progressed. This simple cubic lattice was evident in the terminal nanostructure of the membrane surface (Fig.…”

Section: Introductionmentioning

confidence: 99%

Fit-for-purpose block polymer membranes molecularly engineered for water treatment

et al. 2018

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Continued stresses on fresh water supplies necessitate the utilization of non-traditional resources to meet the growing global water demand. Desalination and hybrid membrane processes are capable of treating non-traditional water sources to the levels demanded by users. Specifically, desalination can produce potable water from seawater, and hybrid processes have the potential to recover valuable resources from wastewater while producing water of a sufficient quality for target applications. Despite the demonstrated successes of these processes, state-of-the-art membranes suffer from limitations that hinder the widespread adoption of these water treatment technologies. In this review, we discuss nanoporous membranes derived from self-assembled block polymer precursors for the purposes of water treatment. Due to their well-defined nanostructures, myriad chemical functionalities, and the ability to molecularly-engineer these properties rationally, block polymer membranes have the potential to advance water treatment technologies. We focus on block polymer-based efforts to: (1) nanomanufacture large areas of highperformance membranes; (2) reduce the characteristic pore size and push membranes into the reverse osmosis regime; and (3) design and implement multifunctional pore wall chemistries that enable solute-specific separations based on steric, electrostatic, and chemical affinity interactions. The use of molecular dynamics simulations to guide block polymer membrane design is also discussed because its ability to systematically examine the available design space is critical for rapidly translating fundamental understanding to water treatment applications. Thus, we offer a full review regarding the computational and experimental approaches taken in this arena to date while also providing insights into the future outlook of this emerging technology.

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Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

Cited by 51 publications

References 19 publications

Block Copolymer Membranes for Aqueous Solution Applications

Block Copolymer Membranes for Aqueous Solution Applications

Design of block copolymer membranes using segregation strength trend lines

Fit-for-purpose block polymer membranes molecularly engineered for water treatment

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