Asymmetric Solvent‐Annealed Triblock Terpolymer Thick Films Topped by a Hexagonal Perforated Lamellar Nanostructure

Aissou, Karim; Bouzit, Hana; Krusch, Felix; Méricq, J.P.; Cot, Didier; Masquelez, Nathalie; Roualdès, S.; Quémener, Damien

doi:10.1002/marc.202100585

Cited by 5 publications

(6 citation statements)

References 29 publications

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“…International Journal of Polymer Science terpolymer material. From this GISAXS pattern, the unit cell of the DG structure (a G ) was determined to be 75.8 nm, based on the diffracted (202) peak at q y, 202 ∼0.234 nm −1 (a G = 2π × 2√2 /q y, 202 ), while the period of the (121) plane was estimated to be 30. behavior has been also observed in previous studies [17,23,24]. Interestingly, the SEM image in Figure 4(d) shows that the DG structure on the bottom surface is not clearly visible compared to the well-developed double wave pattern produced on the top surface (see inset).…”

Section: Resultssupporting

confidence: 84%

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Nanoporous Double-Gyroid Structure from ABC Triblock Terpolymer Thick Films

Aissou,

Coronas,

Hermida-Merino

et al. 2023

International Journal of Polymer Science

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The creation of nanostructured materials with a triply periodic minimal surface (TPMS), defined as a zero mean curvature surface having periodicity in three-dimensional space, is an emerging solution to optimize transport (i.e., the ion-conductivity and hydraulic permeability) through the next-generation of electrolyte and ultrafiltration (UF) membranes. Here, we used an amphiphilic ABC-type block copolymer (BCP) (namely, polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO)) to generate symmetric thick films (~8 μm) composed entirely of a TPMS-based structure, consisting of a PS matrix with a double gyroid (DG) minimal surface and hydrophilic stimuli-responsive (P2VP/PEO) nanochannels. To produce the core/shell DG-structured monoliths, we used a process combining the nonsolvent-induced phase separation (NIPS) process with a solvent vapor annealing (SVA) treatment. From such symmetric ABC-type BCP-thick films generated by NIPS-SVA, a mean hydraulic permeability as high as 514 L h-1 m-2 bar-1 was measured. This mean value was revealed to be nearly equal to that of asymmetric PS-b-P2VP-b-PEO membranes manufactured by NIPS, which have a substructure with an implicit irregular and random distribution of the internal pore structure and a skin layer with P2VP/PEO nanopores arranged into a hexagonal array.

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Section: Resultssupporting

confidence: 84%

“…To extend the comparison, we recently studied the permeability of blended PS-b-P2VP-b-PEO symmetric membranes composed entirely of a hexagonal perforated lamellar (HPL) phase [24]. These 9 μm-thick PS-b-P2VPb-PEO monoliths blended with 20 wt.…”

Section: Resultsmentioning

confidence: 99%

Nanoporous Double-Gyroid Structure from ABC Triblock Terpolymer Thick Films

Aissou,

Coronas,

Hermida-Merino

et al. 2023

International Journal of Polymer Science

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“…Prior to do the measurement, the PS-b-P2VP-b-PNIPAM monoliths generated by NIPS-SVA were deposited on a highly permeable polyvinylidene difluoride (PVDF) support and the permeance was then plotted as the function of the water pressure applied from 0.5 to 2 bar, using a dead-end stirred ultrafiltration cell. 23 The PS-b-P2VP-b-PNIPAM monoliths demonstrated an excellent stability over failure even at high feed pressure (over 2 bar) since a linear change in water flux with the increase in pressure drop is observed regardless of the temperature (20 C and 46 C). Water permeance values were measured to be $2 and 18 L h À1 m À2 .bar À1 at 20 C and viscosity corrected at 46 C, respectively, which demonstrates the thermosensitive character of the PL-structured monoliths.…”

Section: Resultsmentioning

confidence: 93%

“…Note that the NIPS process was initially used to generate asymmetric terpolymer films after the SVA treatment. 23 However, a long SVA time (> 2h) was required to achieve well-defined nanopores on the material top surface, making that only symmetric terpolymer films entirely composed of the PL phase were finally considered in this work.…”

Section: Synthesis Of the Ps-b-p2vp Macro-raft Agentmentioning

confidence: 99%

“…The scattering vector and the sample to detector distance were calibrated using silver behenate as standard, obtaining a sample-to-detector distance of 7500 mm.Water flux performances:The water permeability of the different PS-b-P2VP-b-PNIPAM thick films was measured in a 10 mL filtration cell (Amicon 8010 stirred cell) connected to a water reservoir and a compressed air line. The measurements were performed on 2.5cm diameter PS-b-P2VP-b-PNIPAM material discs supported by a high permeable hydrophilic PVDF material (water permeability of 2900 L h -1 m -2 bar -1 )23 at pressures between 0.5 and 2 bar. The mass of water passing through the stacked materials (permeate) was recorded using a connected balance at regular time intervals for 10 min.…”

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Double stimuli‐responsive perforated lamellar structure formed by linear ABC triblock terpolymer monoliths

Bouzit

Krusch

Hermida‐Merino

et al. 2022

Journal of Polymer Science

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Amphiphilic block copolymer (BCP) thick films with stimuli-responsive pores are promising candidates for the manufacturing of next-generation ultrafiltration (UF) membranes since their smart nanochannels facilitates the removal of fouling which is considered as one of the biggest challenges in membrane technology. In this work, a well-defined polystyrene-blockpoly(2-vinylpyridine)-block-poly(N-isopropylacrylamide) (PS-b-P2VP-b-PNIPAM) terpolymer was prepared for the first time via reversible addition-fragmentation chain transfer (RAFT) polymerization. The combination of the nonsolvent-induced phase separation (NIPS) process with a solvent vapor annealing (SVA) treatment was used to produce nanostructured pH-and thermo-double sensitive ABC-type BCP thick films. Here, the NIPS-made PS-b-P2VPb-PNIPAM thick film, comprising a microporous spinodal-type network substructure, topped by a dense thin layer of poorly defined nanopores is transformed into a monolith entirely composed of a well-ordered perforated lamellar (PL) phase upon exposure to a chloroform vapor during 6h. Such kind of PL-structured monoliths, showing a permeance value as high as 18 L.h -1 .m -².bar -1 at 46°C and pH = 7 with an excellent temperature cyclability, are highly desired to manufacture smart separation-based UF materials able to transit their pore state from hydrophilic to hydrophobic (and vice versa), thereby leading to much more efficient detachment of foulants during the cleaning process.

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Square arrays of vertically aligned nanoporous cylinders from a linear ABC triblock terpolymer

Aissou

Mumtaz

Hermida‐Merino

et al. 2023

Journal of Polymer Science

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Vertically oriented nanoporous cylinders, demonstrating an unprecedented alignment persistence, were produced within freestanding poly(1,1-dimethyl silacyclobutane)-block-polystyrene-block-poly(2-vinyl pyridine) (PDMSB-b-PSb-P2VP) layers ($15 μm thick) blended with short PS-b-P2VP chains by combining the non-solvent induced phase separation (NIPS) process with a solvent vapor annealing (SVA) treatment. Here, the NIPS step allowed for the formation of an asymmetric and porous PDMSB-b-PS-b-P2VP film having a top surface exhibiting poorly-defined nanopores while the subsequent SVA treatment enabled to produce a symmetric layer that possesses highly-ordered cylindrical nanodomains arranged into a 27 nm period square array. As the unblended NIPS/SVA-made PDMSB-b-PS-b-P2VP monoliths exhibited a mixed orientation of parallel and perpendicular cylinders, a blending strategy was used to achieve tetragonally-packed PDMSB and P2VP nanodomains having an exceptional vertical alignment persistence. Such solvent-annealed (3 h, CHCl 3 ) PDMSB-b-PS-b-P2VP monoliths blended with 20 wt% of PS-b-P2VP chains showed a water permeance close to the value measured through their parent NIPS-made terpolymer films having poorly-ordered nanopores.block copolymer membrane, long-range order, self-assembly, solvent vapor annealing, vertical alignment | INTRODUCTIONDense arrays of monodisperse nanodomains having a perpendicular orientation and physical continuity through the entire material thickness are highly-desired in diverse nanotechnology-related applications, including next-generation of electrolytes 1-4 and isoporous membranes. [5][6][7][8][9] For instance, the perfect separation of proteins and viruses having a diameter of tens of nanometers is still challenging, and requires, for a practical use, ultrafiltration

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Asymmetric Solvent‐Annealed Triblock Terpolymer Thick Films Topped by a Hexagonal Perforated Lamellar Nanostructure

Cited by 5 publications

References 29 publications

Nanoporous Double-Gyroid Structure from ABC Triblock Terpolymer Thick Films

Nanoporous Double-Gyroid Structure from ABC Triblock Terpolymer Thick Films

Double stimuli‐responsive perforated lamellar structure formed by linear ABC triblock terpolymer monoliths

Square arrays of vertically aligned nanoporous cylinders from a linear ABC triblock terpolymer

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