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Asymmetric block copolymer membrane fabrication mechanism through self-assembly and non-solvent induced phase separation (SNIPS) process.

ABSTRACT: In this paper, the concept of the functional mechanism of copolymer membrane formation is explained and analyzed from the theoretical and experimental points of view. To understand the phase inversion process and control the final membrane morphology, styrene-acrylonitrile copolymer (SAN) membrane morphology through the self-assembly phenomena is investigated. Since the analysis of the membrane morphology requires the study of both thermodynamic and kinetic parameters, the effect of different membrane formation conditions is investigated experimentally; In order to perceive the formation mechanism of the extraordinary structure membrane, a thermodynamic hypothesis is also developed based on the hydrophilic coil migration to the membrane surface. This hypothesis is analyzed according to Hansen Solubility Parameters and proved using EDX, SAXS, and contact angle analysis of SAN25. Moreover, the SAN30 membrane is fabricated under different operating conditions to evaluate the possibility of morphological prediction based on the developed hypothesis.

SUBMITTER: Hamta A

PROVIDER: S-EPMC8760277 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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Asymmetric block copolymer membrane fabrication mechanism through self-assembly and non-solvent induced phase separation (SNIPS) process.

Hamta Afshin A Ashtiani Farzin Zokaee FZ Karimi Mohammad M Moayedfard Sareh S

Scientific reports 20220114 1

In this paper, the concept of the functional mechanism of copolymer membrane formation is explained and analyzed from the theoretical and experimental points of view. To understand the phase inversion process and control the final membrane morphology, styrene-acrylonitrile copolymer (SAN) membrane morphology through the self-assembly phenomena is investigated. Since the analysis of the membrane morphology requires the study of both thermodynamic and kinetic parameters, the effect of different me ...[more]

PMID: 35031674

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Project description:The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and time-consuming endeavor owing to the high kinetic penalties associated with long polymer chain entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-block-poly(2-vinylpyridine) BCP system (M w: ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕs). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕs value of ∼0.80-0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕs value was found to be greater for films with higher dry thickness (D 0) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕs, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕs values of ∼0.67 and D 0 values of 59-110 nm. This HPL phase can be controllably induced into an order-order transition to a lamellar morphology upon further increase of ϕs to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕs up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕs value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕs does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.

Dataset Information

Asymmetric block copolymer membrane fabrication mechanism through self-assembly and non-solvent induced phase separation (SNIPS) process.

Publications

Asymmetric block copolymer membrane fabrication mechanism through self-assembly and non-solvent induced phase separation (SNIPS) process.

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