Solvent and pH Stability of Poly(styrene-alt-maleic acid) (PSaMA) Membranes Prepared by Aqueous Phase Separation (APS)

In the single-polyelectrolyte aqueous phase separation (APS) approach, membranes are prepared by precipitating a weak polyelectrolyte from a concentrated aqueous solution using a pH switch. This has proven to be a versatile and more sustainable method compared to conventional approaches as it significantly reduces the use of organic solvents. Poly(styrene-alt-maleic acid) (PSaMA) is a polymer that has been extensively investigated for APS and has been the basis for both open and dense membranes with good performances. These membranes are chemically crosslinked and, in this work, we further investigated ultrafiltration (UF) and nanofiltration (NF) membranes prepared with PSaMA for their stability in various organic solvents and under different pH conditions. It was shown that these membranes had stable performances in both isopropanol (IPA) and toluene, and a slightly reduced performance in N-methyl-2-pyrollidone (NMP). However, PSaMA did not perform well as a selective layer in these solvents, indicating that the real opportunity would be to use the UF-type PSaMA membranes as solvent-stable support membranes. Additionally, the membranes proved to be stable in an acidic-to-neutral pH regime (pH 2–7); and, due to the pH-responsive nature of PSaMA, for the NF membranes, a pH-dependent retention of Mg2+ and SO42− ions was observed and, for the UF membranes, a strong responsive behavior was observed, where the pH can be used to control the membrane permeability. However, long-term exposure to elevated pH conditions (pH 8–10) resulted in severe swelling of the NF membranes, resulting in defect formation, and compaction of the UF membranes. For the UF membranes, this compaction did prove to be reversible for some but not all of the membrane samples measured. These results showed that in aqueous systems, membranes prepared with PSaMA had interesting responsive behaviors but performed best at neutral and acidic pH values. Moreover, the membranes exhibited excellent stability in the organic solvents IPA and toluen

Stable Polyelectrolyte Multilayer-Based Hollow Fiber Nanofiltration Membranes for Produced Water Treatment

Produced water (PW) constitutes a massive environmental issue due to its huge global production as well as its complexity and toxicity. Membrane technology could, however, convert this complex waste stream into an important source of water for reuse, but new and more efficient membranes are required. In particular, in the last few years, polyelectrolyte multilayers (PEMs) established themselves as a very powerful method to prepare hollow fiber-based nanofiltration (NF) membranes, and this membrane type and geometry would be ideal for PW treatment. Unfortunately, the presence of surfactants in PW can affect the stability of polyelectrolyte multilayers. In this work, we investigate the stability of polyelectrolyte multilayers toward different types of surfactant, initially on model surfaces. We find that chemically stable multilayers such as poly(diallyldimethylammonium chloride) (PDADMAC)/poly(sodium 4-styrenesulfonate) (PSS), based only on electrostatic interactions, are substantially desorbed by charged surfactants. For poly(allylamine hydrochloride) (PAH)/PSS multilayers, however, we demonstrate that chemical cross-linking by glutaraldehyde leads to surfactant stable layers. These stable PEM coatings can also be applied on hollow fiber support membranes to create hollow fiber NF membranes dedicated for PW treatment. Increased cross-linking time leads to more stable and more selective separation performance. These newly developed membranes were subsequently studied for the treatment of synthetic PW, consisting of freshly prepared oil-in-water emulsions stabilized by hexade-cyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) in the presence of a mixture of ions. For both types of produced water, the membranes show excellent oil removal (∼100%) and organics removal (TOC reduced up to ∼97%) as well as good divalent ion retentions (∼75% for Ca2+ and up to ∼80% for SO42–). Moreover, we observe a high flux recovery for both emulsions (100% for CTAB and 80% for SDS) and especially for the CTAB emulsion a very low degree of fouling. These stable PEM-based hollow fiber membranes thus allow simultaneous deoiling and removal of small organic molecules, particles, and divalent ions in a single step process while also demonstrating excellent membrane cleanability

Asymmetric polyelectrolyte multilayer membranes:Influence of bottom section polycation on layer growth and retention mechanisms

It has been previously demonstrated that asymmetric polyelectrolyte multilayer (PEM) membranes are highly promising for use in water treatment due to their ability to combine a high selectivity with a high permeability. This is achieved by first coating a more open (highly permeable) bottom PEM to fill the pores of the support membrane, and subsequently a more dense (highly selective) top PEM. However, fundamental understanding on the interaction between top and bottom PEM section and the effect of the bottom section on the resulting membrane properties is still lacking. In this study, symmetric membranes with different polycations are prepared and compared with asymmetric membranes which contain an additional poly (allylamine hydrochloride)/poly (acryl amide) (PAH/PAA) top section. PEM layer growth was first studied with optical reflectometry, demonstrating that the growth of the top PEM section is dependent on the previously deposited bottom PEM section. Membrane performance was assessed with cross-flow measurements, where permeability and molecular weight cutoff (MWCO) measurements showed distinct differences for the symmetric membranes. Although these properties converge upon coating of the top section, differences remain. This can be explained by a contribution of the bottom section to hydraulic resistance and by intermixing of the top and bottom section. The degree of intermixing is attributed to differences in mobility of the used polycations. Single salt retention measurements even show that changing the bottom section polycation allows for tuning of the salt retention mechanism of the resulting asymmetric membranes. Whereas membranes with PAH in the bottom section are dominated by dielectric exclusion, membranes with Poly (vinylbenzyltrimethylammonium chloride) (PVBTMAC) in the bottom section show a dominant Donnan exclusion. These observations were confirmed by varying both the salt concentration and the operational flux. Overall, our work demonstrates that asymmetric coating on different bottom PEM chemistries can be used as a promising tuning parameter in layer-by-layer coating. This allows for a more rational design of asymmetric PEM membranes, opening opportunities for tuning membranes towards specific applications.</p

Combined Electrospinning-Electrospraying for High-Performance Bipolar Membranes with Incorporated MCM-41 as Water Dissociation Catalysts

Electrospinning has been demonstrated as a very promising method to create bipolar membranes (BPMs), especially as it allows three-dimensional (3D) junctions of entangled anion exchange and cation exchange nanofibers. These newly developed BPMs are relevant to demanding applications, including acid and base production, fuel cells, flow batteries, ammonia removal, concentration of carbon dioxide, and hydrogen generation. However, these applications require the introduction of catalysts into the BPM to allow accelerated water dissociation, and this remains a challenge. Here, we demonstrate a versatile strategy to produce very efficient BPMs through a combined electrospinning-electrospraying approach. Moreover, this work applies the newly investigated water dissociation catalyst of nanostructured silica MCM-41. Several BPMs were produced by electrospraying MCM-41 nanoparticles into the layers directly adjacent to the main BPM 3D junction. BPMs with various loadings of MCM-41 nanoparticles and BPMs with different catalyst positions relative to the junction were investigated. The membranes were carefully characterized for their structure and performance. Interestingly, the water dissociation performance of BPMs showed a clear optimal MCM-41 loading where the performance outpaced that of a commercial BPM, recording a transmembrane voltage of approximately 1.11 V at 1000 A/m2. Such an excellent performance is very relevant to fuel cell and flow battery applications, but our results also shed light on the exact function of the catalyst in this mode of operation. Overall, we demonstrate clearly that introducing a novel BPM architecture through a novel hybrid electrospinning-electrospraying method allows the uptake of promising new catalysts (i.e., MCM-41) and the production of very relevant BPMs.</p

Surfactant-dependent critical interfacial tension in silicon carbide membranes for produced water treatment

During fossil oil extraction, a complex water stream known as produced water (PW), is co-extracted. Membrane treatment makes PW re-use possible, but fouling and oil permeation remain major challenges. In this work, membrane fouling and oil retention of Synthetic PW stabilized with a cationic, anionic, zwitterionic or nonionic surfactant, were studied at various surfactant and salt concentrations. We discuss our results in the framework of the Young-Laplace (YL) equation, which predicts for a given membrane, pressure and oil-membrane contact angle, a critical interfacial tension (IFT) below which oil permeation should occur. We observe such a transition from high to low oil retention with decreasing IFT for the anionic (SDS), cationic (CTAB) and non-ionic (TX) surfactant, but at significantly higher critical IFTs than predicted by YL. On the other side, for the zwitterionic DDAPS we do not observe a drop in oil retention, even at the lowest IFT. The discrepancy between our findings and the critical IFT predicted by YL can be explained by the difference between the measured contact angle and the effective contact angle at the wall of the membrane pores. This leads to a surfactant-dependent critical IFT. Additionally, our results point out that zwitterionic surfactants even at the lowest IFT did not present a critical IFT and exhibited low fouling and low oil permeation.</p