Design Strategies for Forward Osmosis Membrane Substrates with Low Structural Parameters-A Review.

This article reviews the many innovative strategies that have been developed to specifically design the support layers of forward osmosis (FO) membranes. Forward osmosis (FO) is one of the most viable separation technologies to treat hypersaline wastewater, but its successful deployment requires the development of new membrane materials beyond existing desalination membranes. Specifically, designing the FO membrane support layers requires new engineering techniques to minimize the internal concentration polarization (ICP) effects encountered in cases of FO. In this paper, we have reviewed several such techniques developed by different research groups and summarized the membrane transport properties corresponding to each approach. An important transport parameter that helps to compare the various approaches is the so-called structural parameter (S-value); a low S-value typically corresponds to low ICP. Strategies such as electrospinning, solvent casting, and hollow fiber spinning, have been developed by prior researchers-all of them aimed at lowering this S-value. We also reviewed the quantitative methods described in the literature, to evaluate the separation properties of FO membranes. Lastly, we have highlighted some key research gaps, and provided suggestions for potential strategies that researchers could adopt to enable easy comparison of FO membranes.

A Self-Consistent Model for Sorption and Transport in Polyimide-Derived Carbon Molecular Sieve Gas Separation Membranes.

Demand for energy-efficient gas separations exists across many industrial processes, and membranes can aid in meeting this demand. Carbon molecular sieve (CMS) membranes show exceptional separation performance and scalable processing attributes attractive for important, similar-sized gas pairs. Herein, we outline a mathematical and physical framework to understand these attributes. This framework shares features with dual-mode transport theory for glassy polymers; however, physical connections to CMS model parameters differ from glassy polymer cases. We present evidence in CMS membranes for a large volume fraction of microporous domains characterized by Langmuir sorption in local equilibrium with a minority continuous phase described by Henry's law sorption. Using this framework, expressions are provided to relate measurable parameters for sorption and transport in CMS materials. We also outline a mechanism for formation of these environments and suggest future model refinements.

Carbon Molecular Sieve Membrane Preparation by Economical Coating and Pyrolysis of Porous Polymer Hollow Fibers.

Dip coating and pyrolysis processes are used to create multi-layer asymmetric carbon molecular sieve (CMS) hollow fiber membranes with excellent gas separation properties. Coating of an economical engineered support with a high-performance polyimide to create precursor fibers with a dense skin layer reduces material cost by 25-fold compared to monolithic precursors or ceramic supports. CMS permeation results with CO2 /CH4 (50:50) mixed gas feed show attractive CO2 /CH4 selectivity of 58.8 and CO2 permeance of 310 GPU at 35 °C.

Synchronous Generation of Nano- and Microscaled Hierarchical Porous Polyelectrolyte Multilayers for Superwettable Surfaces.

We created both a superhydrophilic polymer surface and a superhydrophobic surface by using the poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) multilayers with the synchronously generated hierarchical porous surface structures. The formation of surface and pore structures induced at acidic pH values is subject to the composition, distribution, and molecular weights of polyelectrolytes in the layer-by-layer (LbL) assembled film, leading to a variety of unique surface topographies and porous structures located on different scales. During the porous induction at pH 2.0, both nano- and microscaled features synchronously developed on the surface as a result of the unique combination of high-molecular-weight PAH (900K g/mol) and low molecular weight PAA (15K g/mol), along with a much reduced deposition time of 1 min. Although thermally cross-linked, the porous surface with hierarchical structure could achieve superhydrophilicity due to the remaining free amine and carboxylate groups on the porous structures. A complete switch from the superhydrophilic to the superhydrophobic surface was achieved via a simple chemical vapor deposition of trichloro(1H,1H,2H,2H-perfluoro-octyl)silane. In this work, the effects of molecular weight of polyelectrolytes (15K-900K g/mol), deposition time (10-900 s) during the LbL assembly, and pH (1.8 to 2.4) for the porous induction on the surface topography, pore structures, and wetting behavior were investigated in detail. A variety of unique porous surface structures on different length scales were systematically studied by controlling the above parameters.

Development of Layered Multiscale Porous Thin Films by Tuning Deposition Time and Molecular Weight of Polyelectrolytes.

This work focuses on the design of porous polymeric films with nano- and micro-sized pores existing in distinct zones. The porous thin films are fabricated by the post-treatment of layer-by-layer assembled poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) multilayers. In order to improve the processing efficiency, the deposition time is shortened to ≈ 10 s. It is found that fine porous structures can be created even by significantly reducing the processing time. The effect of using polyelectrolytes with widely different molecular weights is also studied. The pore size is increased by using high molecular weight PAH, while high molecular weight PAA minimizes the pore size to nanometer scale. Having gained a precise control over the pore size, layered multiscale porous thin films are further built up with either a microsized porous zone on top of a nanosized porous zone or vice versa.

Recent progress in the applications of layer-by-layer assembly to the preparation of nanostructured ion-rejecting water purification membranes.

Reverse osmosis (RO) and nanofiltration (NF) are the two dominant membrane separation processes responsible for ion rejection. While RO is highly efficient in removal of ions it needs a high operating pressure and offers very low selectivity between ions. Nanofiltration on the other hand has a comparatively low operating pressure and most commercial membranes offer selectivity in terms of ion rejection. However in many nanofiltration operations rejection of monovalent ions is not appreciable. Therefore a high flux high rejection membrane is needed that can be applied to water purification systems. One such alternative is the usage of polyelectrolyte multilayer membranes that are prepared by the deposition of alternately charged polyelectrolytes via layer-by-layer (LbL) assembly method. LbL is one of the most common self-assembly techniques and finds application in various areas. It has a number of tunable parameters like deposition conditions, number of bilayers deposited etc. which can be manipulated as per the type of application. This technique can be applied to make a nanothin membrane skin which gives high rejection and at the same time allow a high water flux across it. Several research groups have applied this highly versatile technique to prepare membranes that can be employed for water purification. Some of these membranes have shown better performance than the commercial nanofiltration and reverse osmosis membranes. These membranes have the potential to be applied to various different aspects of water treatment like water softening, desalination and recovery of certain ions. Besides the conventional method of LbL technique other alternative methods have also been suggested that can make the technique fast, more efficient and thereby make it more commercially acceptable.

Conductive oxygen barrier films using supramolecular assembly of graphene embedded polyelectrolyte multilayers.

The supramolecular self-assembly of polyelectrolyte multilayers (PEMs) provides robust bottom-up strategies to assemble a broad spectrum of nanostructures on the host substrates. In this study, we discuss the formation of graphene nanoplatelet (GNP) embedded polyelectrolyte films to enhance the oxygen barrier properties of poly(ethylene terephthalate) (PET) films. Despite cheaper costs and high mechanical strength, the diffusion of small gas molecules such as oxygen through PET films remains a matter of great concern. The simple yet robust supramolecular deposition of GNP/polyelectrolyte on PET substrates significantly increases the tortuous path the oxygen molecule has to travel, making it harder to diffuse through the PET film. With permeability coefficients in the range of 10-18 cc cm/cm(2) s Pa, the coatings developed in this study show three orders of magnitude reduction as compared to the permeability coefficient of the bare PET film, significantly lower than that of ethylene vinyl alcohol (EVOH) and comparable to silicon oxide thin films used in commercial gas barrier foils. The use of GNPs in the multilayered films also helped reduce the electrical sheet resistance to about 1MΩ which is five orders of magnitude lower than the original PET substrate opening up promising opportunities for future use in semiconductor and electronics industry. Making suitable modifications in the deposition process, three configurations of GNP embedded PEM multilayers namely hydrogen bonded, electrostatic, and composite films were developed and their effect on oxygen barrier property and sheet resistance was monitored. Oxygen permeability of films was tested in accordance with ASTM D-3985 using a MOCON 2/21 ML instrument, whereas electrical sheet resistance was quantified using a Gamry Femtostat Electrochemical Impedance station.