Nondestructive Creation of Ordered Nanopores by Selective Swelling of Block Copolymers: Toward Homoporous Membranes.

Abstract

Pores regulate the entry and exit of substances based on the differences in physical sizes or chemical affinities. Pore uniformity, ordering, and the homogeneity of the surface chemistry of the pore walls are vital for maximizing the performance of a porous material because any scattering in these parameters weakens the capability of pores to discriminate foreign substances. Most strategies for the creation of homogeneous pores are destructive, and sacrificial components in the precursor materials must be selectively removed to generate porosities. The incorporation and subsequent removal of the sacrificial components frequently make the pore-making process complicated and inefficient and impose greater uncertainty in the control of the pore homogeneity. Block copolymers (BCPs) have been demonstrated to be promising precursors in the fabrication of highly ordered nanoporous structures. Unfortunately, BCP-derived porosities are also predominantly dependent on destructive pore-making processes (e.g., etching or extraction). To address this problem, we have developed a swelling-based nondestructive strategy. In this swelling process, one simply needs to immerse BCP materials in a solvent selective for the minority blocks for hours. After removing the BCPs from the solvent followed by air drying, pores are generated throughout the BCP materials in the positions where the minority blocks initially dwell. This Account discusses our recent discoveries, new insights, and emerging applications of this burgeoning pore-making method with a focus on the development of ordered porosities in bulk BCP materials. The initial morphology and orientation of the minority phases in BCPs determine the pore orientation and geometry in the produced porous materials. For nonaligned BCPs, three-dimensionally interconnected pores with sizes scattering in the 10-50 nm range are produced after swelling. There is a morphology evolution of BCP materials from the initial nonporous structure to the increasingly opened nanoporous intermediates, to interconnected networks of micellar nanofibers, and finally to isolated micellar spheres with increasing degrees of swelling. When the BCP films are aligned perpendicularly or in-plane, selective swelling results in uniform "standing" (perpendicular orientation) and "sleeping" (in-plane orientation) pores, respectively. Pore sizes can be tuned by changing molecular weights of the BCPs and swelling conditions without the loss of pore uniformity. Due to the nondestructive nature of this swelling process, nothing in the BCPs is lost during the pore-forming procedure, and consequently the formed pores can be progressively closed also by selective swelling. Such reversible pore opening/closing can be repeated many times, enabling the application of these materials in drug delivery and intelligent antireflective coatings. The monodispersed pore sizes, straight pore profile, and hydrophilic pore walls particularly favor the application of the porous BCPs in separations as homoporous membranes (HOMEs) exhibiting high selectivity, permeability, and inherent stimulus responsiveness.