We demonstrate the fabrication of a loose, negatively charged nanofiltration (NF) membrane with tailored selectivity for the removal of perfluoroalkyl substances with reduced scaling potential. A selective polyamide layer was fabricated on top of a polyethersulfone support via interfacial polymerization of trimesoyl chloride and a mixture of piperazine and bipiperidine. Incorporating high molecular weight bipiperidine during the interfacial polymerization enables the formation of a loose, nanoporous selective layer structure. The fabricated NF membrane possessed a negative surface charge and had a pore diameter of ~1.2 nm, much larger than a widely used commercial NF membrane (i.e., NF270 with pore diameter of ~0.8 nm). We evaluated the performance of the fabricated NF membrane for the rejection of different salts (i.e., NaCl, CaCl2, and Na2SO4) and perfluorooctanoic acid (PFOA). The fabricated NF membrane exhibited a high retention of PFOA (~90%) while allowing high passage of scale-forming cations (i.e., calcium). We further performed gypsum scaling experiments to demonstrate lower scaling potential of the fabricated loose porous NF membrane compared to NF membranes having a dense selective layer under solution conditions simulating high water recovery. Our results demonstrate that properly designed NF membranes are a critical component of a high recovery NF system, which provide an efficient and sustainable solution for remediation of groundwater contaminated with perfluoroalkyl substances.

There is long-standing interest in developing membranes possessing uniform pores with dimensions in the range of 1 nm and physical continuity in the macroscopic transport direction to meet the needs of challenging small molecule and ionic separations. Here we report facile, scalabe fabrication of polymer membranes with vertically (i.e., along the through-plane direction) aligned 1 nm pores by magnetic-field alignment and subsequent cross-linking of a liquid crystalline mesophase. We utilize a wedge-shaped amphiphilic species as the building block of a thermotropic columnar mesophase with 1 nm ionic nanochannels, and leverage the magnetic anisotropy of the amphiphile to control the alignment of these pores with a magnetic field. In situ X-ray scattering and subsequent optical microscopy reveal the formation of highly ordered nanostructured mesophases and cross-linked polymer films with orientational order parameters of ca. 0.95. High-resolution transmission electron microscopy (TEM) imaging provides direct visualization of long-range persistence of vertically aligned, hexagonally packed nanopores in unprecedented detail, demonstrating high-fidelity retention of structure and alignment after photo-cross-linking. Ionic conductivity measurements on the aligned membranes show a remarkable 85-fold enhancement of conductivity over nonaligned samples. These results provide a path to achieving the large area control of morphology and related enhancement of properties required for high-performance membranes and other applications.

An ethanol-based Pickering emulsion that spontaneously forms conductive composites is used to sustainably manufacture compliant strain sensors.

We examine the influence of magnetic fields on the order-disorder transition (ODT) in a liquid crystalline block copolymer. This is motivated by a desire to understand the dynamics of microstructure alignment during field annealing as potentially dictated by selective destabilization of nonaligned material. Temperature resolved scattering across the ODT and time-resolved measurements during isothermal field annealing at sub-ODT temperatures were performed in situ. Strongly textured mesophases resulted in each case but no measurable field-induced shift in $T_{\mathrm{ODT}}$ was observed. This suggests that selective melting does not play a discernable role in the system’s field response. Our data indicate instead that alignment occurs by slow grain rotation within the mesophase. We identify an optimum subcooling that maximizes alignment during isothermal field annealing. This is corroborated by a simple model incorporating the competing effects of an exponentially decreasing mobility and divergent, increasing magnetic anisotropy on cooling below $T_{\mathrm{ODT}}$. The absence of measurable field effects on $T_{\mathrm{ODT}}$ is consistent with estimates based on the relative magnitudes of the field interaction energy and the enthalpy associated with the ODT.