ABSTRACT
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 toluene.
ABSTRACT
Aqueous phase separation (APS) is a recently developed sustainable alternative to the conventional organic solvent based nonsolvent-induced phase separation (NIPS) method to prepare polymeric membranes. In APS, polyelectrolytes are precipitated from aqueous solutions through pH or salinity switches. Although APS differs from NIPS in the polymer and solvents, they share many tuning parameters. In this work, we investigate the APS-based preparation of membranes from poly(styrene-alt-maleic acid) (PSaMA) with a focus on acid concentration in the coagulation bath, and polymer and additive concentration in the casting solution. Nanofiltration membranes are prepared using significantly lower concentrations of acid: 0.3 M HCl compared to the 2 M of either acetic or phosphoric acid used in previous works. It is shown that higher polymer concentrations can be used to prevent defect formation in the top layer. In addition, acetic acid concentration also strongly affects casting solution viscosity and thus can be used to control membrane structure, where lower acetic acid concentrations can prevent the formation of macrovoids in the support structure. The prepared nanofiltration membranes exhibit a very low molecular weight cutoff (210 ± 40 dalton), making these sustainable membranes very relevant for the removal of contaminants of emerging concern. Understanding how the parameters described here affect membrane preparation and performance is essential to optimizing membranes prepared with APS towards this important application.
ABSTRACT
HYPOTHESIS: Salt identity and concentration affects the preparation of membranes via the aqueous phase separation approach. The phase inversion process and morphology of the resultant membranes is expected to vary as function of these two parameters. EXPERIMENTS: Polymeric membranes based on the responsive copolymer polystyrene-alt-maleic acid (PSaMA) are prepared using the aqueous phase separation approach and the influence of salt identity (Na2SO4, LiCl, NaCl, NaNO3, NH4Cl, MgCl2, CaCl2) and concentration on resultant membrane morphology and separation performance is investigated. Complementary stability experiments of PSaMA solutions are performed to help understand the intricate aqueous phase separation process. FINDINGS: Specific ion effects are observed during membrane formation by the aqueous phase separation approach. At equal ionic strengths, Na2SO4 and LiCl lead to the formation of more open membrane structures compared to NaCl, NaNO3, NH4Cl, and MgCl2, while CaCl2 results in membranes with dense top layers. These ion-specific effects are likely caused by a combination of ion mobility and interaction potential between the ion and the polyelectrolyte. Overall, from this work it becomes clear that salt identity and concentration are key parameters in the APS process, and they can be optimised to tune membrane structure from open microfiltration to dense nanofiltration membranes.
ABSTRACT
Membranes are often used in environmentally friendly applications and as a sustainable alternative to conventional processes. Unfortunately, the vast majority of polymeric membranes are produced via an unsustainable and environmentally unfriendly process that requires large amounts of harsh reprotoxic chemicals such as N-methyl-2-pyrrolidinone and dimethylformamide. In this work, we investigate an aqueous phase separation (APS) system that uses weak polyelectrolytes, whose charge is dependent on the pH (weak polyelectrolytes), to produce membranes. Specifically the copolymer polystyrene-alt-maleic acid (PSaMA) is used. PSaMA contains responsive monomers, required for APS, and also unresponsive hydrophobic monomers that provide mechanical stability to the resultant membranes. This work demonstrates that by controlling the precipitation of PSaMA, it is possible to prepare a wide range of membranes; from microfiltration membranes capable of treating oily waste water to dense nanofiltration-type membranes with excellent micropollutant retentions and high mechanical stability. While similar materials in prior work could only withstand 4 bar, the membranes presented here demonstrate stable operation up to 20 bar. The only solvents used in this APS system are water and the green solvent acetic acid, thus making our APS process significantly more sustainable and environmentally friendly as compared to the conventional membrane fabrication methods.
ABSTRACT
Polymeric membranes are used on huge scales for kidney dialysis, wastewater treatment, and drinking water production. However, almost all polymeric membranes are fabricated by a process reliant on the use of unsustainable, expensive, and reprotoxic dipolar aprotic solvents. In this work, we propose an aqueous phase separation approach for preparing porous membrane films. Poly(4-vinylpyridine) (P4VP), a pH-responsive polymer, is first dissolved at low pH where the polymer is charged and subsequently cast as a thin film. Switching to a high pH where the polymer is uncharged and insoluble results in controlled phase separation and solidification of the polymer into porous membrane structures. This approach gives a large degree of control over membrane structure, leading to symmetric porous microfiltration membranes and asymmetric dense nanofiltration membranes. Moreover, the use of a pH-responsive polymer leads directly to a pH-responsive membrane, where the degree of responsive behavior can be tuned by the degree of cross-linking. Such responsive behavior allows effective cleaning of the membrane, without the use of harsh chemicals. This work outlines an approach toward preparing membranes in a more sustainable fashion-an approach that allows control over the membrane structure and one that naturally leads to advanced membranes with responsive properties.
