Membranes

Produced water (PW) is, by volume, the largest waste product of the oil- and gas-exploration industry and contains pollutants such as hydrocarbons and heavy metals. To meet the stringent environmental regulations, PW must be treated before discharging into the environment. The current study proposes a novel treatment method where PW is used to prepare oil-in-water emulsion with potential applications within the oil-exploration industry. The emulsions are prepared by applying hollow fiber membrane emulsification (ME) on PW, which inherently contains oil, as to-be-dispersed phase. The results demonstrate that the average droplet size of the emulsions is a function of pressure applied on to-be-dispersed phase and could be customized from 0.24 to 0.65 µm by varying the pressure from 0.25 to 1 bar, respectively. Stability of the emulsions was verified under high pressure and a temperature and storage period of more than 24 h. The calculations showed that an ME unit with <100 kg weight and <1 m³ volume is appropriate to transform the daily average volume of PW from the Danish part of the North Sea into the emulsions. The study provides a novel route, which also complies well with the requirements (low-weight and small spatial footprints) of the offshore oil rigs, to treat and reuse PW within the oil production process and, therefore, eliminates its environmental footprint. Full article

Desalination is an opportunity to get fresh water for irrigation and for drinking. Reverse Osmosis (RO) for sea water desalination is a solution for the high demand for water in Atlantic islands. The most efficient process to get desalinated water is RO; however, it is necessary to study what to do with the RO membranes used at the end of their life. This paper confirms the possibility to recycle them. The main categories of recycling by thermal processing commonly used in the industry include incineration and pyrolysis to produce energy, gas and fuel. These processes can be applied to mixed plastic waste, such as the combination of materials used in the manufacture of RO membranes. Recycling RO elements from desalination plants is shown to be an opportunity and pioneering initiatives are already underway in Europe. Energy recovery, via incineration, is feasible nowadays and it is a possibility to recycle RO membranes. On the other hand, the recycling of RO elements, via the pyrolytic industry, for fuel production could be centralized in a new industry already planned in the Macaronesia area and all obsolete osmosis membranes could be sent there for recycling. Recycling RO membranes is a very important opportunity for the environment and economy of the zone. This is a new business in water treatments with membranes, very interesting for decreasing the residues and the carbon footprint. The importance of this work is applied to sea water membranes, brackish water ones, and also wastewater tertiaries RO elements at the end of their life. Full article

The electrochemical synthesis of ammonia through the nitrogen reduction reaction (NRR) is receiving much attention, since it is considered a promising alternative to the Haber–Bosch process. In NRR experiments, a Nafion membrane is generally adopted as a separator. However, its use is controversial since ammonia can be trapped in the membrane, to some extent, or even pass through it. We systematically investigate the interaction of a Nafion membrane with ammonia and with an electrolyte and compare it with Zirfon as a possible alternative separator. We show that Nafion containing ammonia can easily release it when immersed in a 0.1 M Na₂SO₄ ammonia-free electrolyte, due to the cation exchange mechanism (Na⁺-NH₄⁺). Since Na₂SO₄ is a commonly adopted electrolyte for NRR experiments, this may cause serious measurement errors and non-reproducible results. The same experiments performed using the polysulfone Zirfon separator clearly show that it is immune to interactions with ammonia, because of its different ion conduction mechanism. The findings provide a deeper understanding of the choice of membrane and electrolyte to be adopted for NRR tests, and may allow one to obtain more accurate and reliable results. Full article

Since 1 January 2020, the sulfur content allowed in exhaust gas plume generated by marine vessels decreased to 0.5% m/m. To be compliant, a hybrid scrubber was installed on-board, working in closed loop and generating a high volume of alkaline wastewater. The alkaline water suspension was treated by a silicon carbide multitubular membrane to remove pollutants, and to allow the water discharge into the natural environment. In this paper, membrane filtration behavior was analyzed for the maritime scrubber wastewater. A range of operating parameters were obtained for several feedwater quality-respecting industrial constraints. The objective was an improvement of (I) the water recovery rate, (II) the filtration duration, and (III) the permeate quality. Thus, in high-fouling water, a low permeate flow (60 L h⁻¹ m⁻²) with frequent backflushing (every 20 min) was used to maintain membrane performance over time. In terms of water quality, the suspended solids and heavy metals were retained at more than 99% and 90%, respectively. Other seawater discharge criteria in terms of suspended solids concentration, pH, and polyaromatic hydrocarbons were validated. The recommended operating conditions from laboratory study at semi-industrial scale were then implemented on a vessel in real navigation conditions with results in agreement with expectations. Full article

Thin-film composite m embranes (TFC) obtained by the formation of a selective layer on a porous membrane-substrate via interfacial polymerization (IP) are indispensable for separation procedures in reverse osmosis, nanofiltration, pervaporation, and gas separation. Achieving high selectivity and permeability for TFC membranes is still one of the main challenges in membrane science and technology. This study focuses on the development of thin film nanocomposite (TFN) membranes with a hierarchically structured polyamide (PA)/chitosan succinate (ChS) selective layer embedded with a metal–organic framework of iron 1,3,5-benzenetricarboxylate (Fe-BTC) for the enhanced pervaporation dehydration of isopropanol. The aim of this work was to study the effect of Fe-BTC incorporation into the ChS interlayer and PA selective layer, obtained via IP, on the structure, properties, and performance of pervaporation TFN membranes. The structure and hydrophilicity of the developed TFN membranes were investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM), along with water contact angle measurements. The developed TFN membranes were studied in the pervaporation dehydration of isopropanol (12–30 wt % water). It was found that incorporation of Fe-BTC into the ChS interlayer yielded the formation of a smoother, more uniform, and defect-free PA ultrathin selective layer via IP, due to the amorpho-crystalline structure of particles serving as the amine storage reservoir and led to an increase in membrane selectivity toward water, and a slight decrease in permeation flux compared to the ChS interlayered TFC membranes. The best pervaporation performance was demonstrated by the TFN membrane with a ChS-Fe-BTC interlayer and the addition of 0.03 wt % Fe-BTC in the PA layer, yielding a permeation flux of 197–826 g·m⁻²·h⁻¹ and 98.50–99.99 wt % water in the permeate, in the pervaporation separation of isopropanol/water mixtures (12–30 wt % water). Full article

Graphene oxide (GO), a carbonaceous 2D nanomaterial, has received significant interest as a next-generation membrane building block. To fabricate high-performance membranes, an effective strategy involves stacking GO nanosheets in laminated structures, thereby creating unique nanochannel galleries. One outstanding merit of laminar GO membranes is that their permselectivity is readily tunable by tailoring the size of the nanochannels. Here, a high-performance GO-based nanofiltration membrane was developed by intercalating an aromatic crosslinker, α,α/-dichloro-p-xylene (DCX), between the layers in laminated GO nanosheets. Owing to the formation of strong covalent bonds between the crosslinker and the GO, the resulting GO laminate membrane exhibited outstanding structural stability. Furthermore, due to the precisely controlled and enlarged interlayer spacing distance of the developed DCX-intercalated GO membrane, it achieved an over two-fold enhancement in water permeability (11 ± 2 LMH bar⁻¹) without sacrificing the rejection performance for divalent ions, contrary to the case with a pristine GO membrane. Full article

Sodium hypochlorite (NaOCl) is a commonly used cleaning agent for recovering membrane performance in membrane technologies. A thorough understanding of the impacts of NaOCl exposure on membrane properties and fouling behavior is important for optimizing chemical cleaning process and extending membrane lifespan. In this study, three commercial polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membranes (SMM-1010, MEMCOR^® CS Ⅱ and ZeeWeed 500) were used to systematically explore the effects of NaOCl dose and solution pH (8 and 10) on membrane properties. The results showed that membrane pores increased with exposure time prolonging, and more pores were observed at pH 8 aging condition. The amide group in the Fourier transformation infrared spectra was disappeared, while the carboxylic acid and succinimide groups were formed at pH 10 and pH 8 conditions, respectively. The hydrophilicity and pure water permeability (PWP) of SMM-1010 and MEMCOR^® CS Ⅱ membranes had insignificant changes during NaOCl aging process, whereas the hydrophilicity of ZeeWeed 500 membrane slightly decreased and its PWP increased by 1.4-fold. The antifouling properties of NaOCl-aged SMM-1010 and MEMCOR^® CS Ⅱ membranes were slightly improved, whereas the NaOCl-aged ZeeWeed 500 membrane showed severer flux decline with humic acid filtration. Our findings could provide guidance for practical chemical cleaning process optimization. Full article

Despite their potential for the scalable production of mixed-matrix membranes (MMMs), the MMMs prepared by the polymer-modification-enabled in situ metal–organic framework formation (PMMOF) process showed a considerable reduction in gas permeability as the filler loading increased. It was hypothesized that a correlation existed between the decrease in permeability and the change in the properties of the polymer, such as free volume and chain flexibility, upon in situ MOF formation. Herein, we aim to address the permeability reduction by using a cross-linked polyimide (6FDA-DAM:DABA (3:2)). It was found the degree of cross-linking affected not only the properties of the polymer, but also the in situ formation of the ZIF-8 filler particles in the cross-linked polymer. The proper degree of cross-linking resulted in suppressing C₃H₆ permeability reduction, suggesting a possible strategy to overcome the issue of PMMOF. The swelling of the polymer followed by chain rearrangement during the PMMOF, as well as the structural rigidity of the polymer, were found to be critical in mitigating permeability reduction. Full article

In this work, we propose the development of an efficient, economical, automated, and sustainable method for separating bioproducts from culture medium via the integration of a sucrose-secreting cyanobacteria production process and pressure-driven membrane filtration technology. Firstly, we constructed sucrose-secreting cyanobacteria with a sucrose yield of 600^__700 mg/L sucrose after 7 days of salt stress, and the produced sucrose could be fully separated from the cyanobacteria cultures through an efficient and automated membrane filtration process. To determine whether this new method is also economical and sustainable, the relationship between membrane species, operating pressure, and the growth status of four cyanobacterial species was systematically investigated. The results revealed that all four cyanobacterial species could continue to grow after UF filtration. The field emission scanning electron microscopy and confocal laser scanning microscopy results indicate that the cyanobacteria did not cause severe destruction to the membrane surface structure. The good cell viability and intact membrane surface observed after filtration indicated that this innovative cyanobacteria–membrane system is economical and sustainable. This work pioneered the use of membrane separation to achieve the in situ separation of cyanobacterial culture and target products, laying the foundation for the industrialization of cyanobacterial bioproducts. Full article

The spin-lattice relaxation rate (T₁⁻¹) of lipid spin labels obtained from saturation recovery EPR measurements in deoxygenated membranes depends primarily on the rate of the rotational diffusion of the nitroxide moiety within the lipid bilayer. It has been shown that T₁⁻¹ also can be used as a qualitative convenient measure of membrane fluidity that reflects local membrane dynamics; however, the relation between T₁⁻¹ and rotational diffusion coefficients was not provided. In this study, using data previously presented for continuous wave and saturation recovery EPR measurements of phospholipid analog spin labels, one-palmitoyl-2-(n-doxylstearoyl)phosphatidylcholine in 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine/cholesterol membranes, we show that measured T₁⁻¹ values are linear functions of rotational diffusion of spin labels. Thus, these linear relationships can be used to transfer T₁⁻¹ values into spin label rotational rates as a precise description of membrane fluidity. This linearity is independent through the wide range of conditions including lipid environment, depth in membrane, local hydrophobicity, and the anisotropy of rotational motion. Transferring the spin-lattice relaxation rates into the rotational diffusion coefficients makes the results obtained from saturation recovery EPR spin labeling easy to understand and readily comparable with other membrane fluidity data. Full article

A benzimidazole-containing diamine monomer was prepared via a simple one-step synthesis process. A two-step procedure involving polycondensation in the presence of aromatic dianhydrides (4,4′-oxydiphthalic anhydride, ODPA) followed by thermal imidization was then performed to prepare a benzimidazole-based polyimide (BI-PI). BI-PI membranes were fabricated using an electrospinning technique and were hot pressed for 30 min at 200 °C under a pressure of 50 kgf /cm². Finally, the hot-pressed membranes were assembled into supercapacitors, utilizing high-porosity-activated water chestnut shell biochar as the active material. The TGA results showed that the BI-PI polymer produced in the two-step synthesis process had a high thermal stability (T_d5% = 527 °C). Moreover, the hot-press process reduced the pore size in the BI-PI membrane and improved the pore-size uniformity. The hot-press procedure additionally improved the mechanical properties of the BI-PI membrane, resulting in a high tensile modulus of 783 MPa and a tensile strength of 34.8 MPa. The cyclic voltammetry test results showed that the membrane had a specific capacitance of 121 F/g and a capacitance retention of 77%. By contrast, a commercial cellulose separator showed a specific capacitance value of 107 F/g and a capacitance retention of 49% under the same scanning conditions. Finally, the membrane showed both a small equivalent series resistance (R_s) and a small interfacial resistance (R_ct). Overall, the results showed that the BI-PI membrane has significant potential as a separator for high-performance supercapacitor applications. Full article

A recurring motif in soft matter and biophysics is modeling the mechanics of interacting particles on fluid membranes. One of the main outstanding challenges in these applications is the need to model the strong coupling between the substrate deformation and the particles’ positions as the latter freely move on the former. This work presents a thin-shell finite element formulation based on subdivision surfaces to compute equilibrium configurations of a thin fluid shell with embedded particles. We use a variational Lagrangian framework to couple the mechanics of the particles and the substrate without having to resort to ad hoc constraints to anchor the particles to the surface. Unlike established methods for such systems, the particles are allowed to move between elements of the finite element mesh. This is achieved by parametrizing the particle locations on the reference configuration. Using the Helfrich–Canham energy as a model for fluid shells, we present the finite element method’s implementation and an efficient search algorithm required to locate particles on the reference mesh. Several analyses with varying numbers of particles are finally presented reproducing symmetries observed in the classic Thomson problem and showcasing the coupling between interacting particles and deformable membranes. Full article

In this work, the preparation of dense blended membranes, from blends of poly(vinylidene fluoride) (PVDF), poly(ether sulfone) (PES) and polyethyleneimine (PEI) or Fumion^®, with possible applications in alkaline fuel cell (AEMFC) is reported. The blended PEI/Fumion^® membranes were prepared under a controlled air atmosphere by a solvent evaporation method, and were characterized regarding water uptake, swelling ratio, thermogravimetric analysis (TGA), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), ion exchange capacity (IEC), OH⁻ conductivity and novel hydroxide ion exchange rate (HIER), which is related to the mass transport capacity of the OH⁻ ions through the membrane. The effect of the chemical composition on its morphological and anion exchange properties was evaluated. It was expected that the usage of a commercial ionomer Fumion^®, in the blended membranes would result in better features in the electrical/ionic conductivity behaviour. However, two of the membranes containing PEI exhibited a higher HIER and OH⁻ conductivity than Fumion^® membranes, and were excellent option for potential applications in AEMFC, considering their performance and the cost of Fumion^®-based membranes. Full article

This paper presents a comprehensive study of the performance of a newly developed titania nanotube incorporated RO membrane for endocrine-disrupting compound (EDC) removal at a low concentration. EDCs are known as an emerging contaminant, and if these pollutants are not properly removed, they can enter the water cycle and reach the water supply for residential use, causing harm to human health. Reverse osmosis (RO) has been known as a promising technology to remove EDCs. However, there is a lack of consensus on their performance, especially on the feed concentrations of EDC that vary from one source to another. In this study, polyamide thin-film composite (PA TFC) membrane was incorporated with one-dimensional titania nanotube (TNT) to mitigate trade-off between water permeability and solute rejection of EDC. The characterization indicated that the membrane surface hydrophilicity has been greatly increased with the presence of TNT. Using bisphenol A (BPA) and caffeine as model EDC, the removal efficiencies of the pristine TFC and thin-film nanocomposite (TFN) membranes were evaluated. Compared to TFC membrane, the membrane modified with 0.01% of TNT exhibited improved permeability of 50% and 49% for BPA and caffeine, respectively. A satisfactory BPA rejection of 89.05% and a caffeine rejection of 97.89% were achieved by the TNT incorporated TFN membranes. Furthermore, the greater hydrophilicity and smoother surface of 0.01 TFN membrane led to lower membrane fouling tendency under long-term filtration. Full article

Bio-membranes exhibit complex but unique mechanical properties as communicative regulators in various physiological and pathological processes. Exposed to a dynamic micro-environment, bio-membranes can be seen as an intricate and delicate system. The systematical modeling and detection of their local physical properties are often difficult to achieve, both quantitatively and precisely. The recent emerging diamonds hosting quantum defects (i.e., nitrogen-vacancy (NV) center) demonstrate intriguing optical and spin properties, together with their outstanding photostability and biocompatibility, rendering them ideal candidates for biological applications. Notably, the extraordinary spin-based sensing enable the measurements of localized nanoscale physical quantities such as magnetic fields, electrical fields, temperature, and strain. These nanoscale signals can be optically read out precisely by simple optical microscopy systems. Given these exclusive properties, NV-center-based quantum sensors can be widely applied in exploring bio-membrane-related features and the communicative chemical reaction processes. This review mainly focuses on NV-based quantum sensing in bio-membrane fields. The attempts of applying NV-based quantum sensors in bio-membranes to investigate diverse physical and chemical events such as membrane elasticity, phase change, nanoscale bio-physical signals, and free radical formation are fully overviewed. We also discuss the challenges and future directions of this novel technology to be utilized in bio-membranes. Full article

The further development of high temperature polymer electrolyte membrane (HT-PEM) fuel cells largely depends on the improvement of all components of the membrane–electrode assembly (MEA), especially membranes and electrodes. To improve the membrane characteristics, the cardo-polybenzimidazole (PBI-O-PhT)-based polymer electrolyte complex doped with phosphoric acid is reinforced using an electrospun m-PBI mat. As a result, the PBI-O-PhT/es-m-PBI_net · nH₃PO₄ reinforced membrane is obtained with hydrogen crossover values (~0.2 mA cm⁻² atm⁻¹), one order of magnitude lower than the one of the initial PBI-O-PhT membrane (~3 mA cm⁻² atm⁻¹) during HT-PEM fuel cell operation with Celtec^®P1000 electrodes at 180 °C. Just as importantly, the reinforced membrane resistance was very close to the original one (65–75 mΩ cm² compared to ~60 mΩ cm²). A stress test that consisted of 20 start–stops, which included cooling to the room temperature and heating back to 180 °C, was applied to the MEAs with the reinforced membrane. More stable operation for the HT-PEM fuel cell was shown when the Celtec^®P1000 cathode (based on carbon black) was replaced with the carbon nanofiber cathode (based on the pyrolyzed polyacrylonitrile electrospun nanofiber mat). The obtained data confirm the enhanced characteristics of the PBI-O-PhT/es-m-PBI_net · nH₃PO₄ reinforced membrane. Full article

Forward osmosis (FO) is a promising separation technology to overcome the challenges of pressure-driven membrane processes. The FO process has demonstrated profound advantages in treating feeds with high salinity and viscosity in applications such as brine treatment and food processing. This review discusses the advancement of FO membranes and the key membrane properties that are important in real applications. The membrane substrates have been the focus of the majority of FO membrane studies to reduce internal concentration polarization. However, the separation layer is critical in selecting the suitable FO membranes as the feed solute rejection and draw solute back diffusion are important considerations in designing large-scale FO processes. In this review, emphasis is placed on developing FO membrane selective layers with a high selectivity. The effects of porous FO substrates in synthesizing high-performance polyamide selective layer and strategies to overcome the substrate constraints are discussed. The role of interlayer in selective layer synthesis and the benefits of nanomaterial incorporation will also be reviewed. Full article

While potentiometric, plasticized membrane sensors are known as convenient, portable and inexpensive analytical instruments, their development is time- and resource-consuming, with a poorly predictable outcome. In this study, we investigated the applicability of the QSPR (quantitative structure–property relationship) method for predicting the potentiometric sensitivity of plasticized polymeric membrane sensors, using the ionophore chemical structure as model input. The QSPR model was based on the literature data on sensitivity, from previously studied, structurally similar ionophores, and it has shown reasonably good metrics in relating ionophore structures to their sensitivities towards Cu²⁺, Cd²⁺ and Pb²⁺. The model predictions for four newly synthesized diphenylphosphoryl acetamide ionophores were compared with real potentiometric experimental data for these ionophores, and satisfactory agreement was observed, implying the validity of the proposed approach. Full article

Transient Receptor Potential Melastatin 8 (TRPM8) from the melastatin TRP channel subfamily is a non-selective Ca²⁺-permeable ion channel with multimodal gating which can be activated by low temperatures and cooling compounds, such as menthol and icilin. Different conditions such as neuropathic pain, cancer, overactive bladder syndrome, migraine, and chronic cough have been linked to the TRPM8 mode of action. Despite the several potent natural and synthetic inhibitors of TRPM8 that have been identified, none of them have been approved for clinical use. The aim of this study was to discover novel blocking TRPM8 agents using automated patch clamp electrophysiology combined with a ligand-based virtual screening based on the SwissSimilarity platform. Among the compounds we have tested, nebivolol and carvedilol exhibited the greatest inhibitory effect, with an IC₅₀ of 0.97 ± 0.15 µM and 9.1 ± 0.6 µM, respectively. This study therefore provides possible candidates for future drug repurposing and suggests promising lead compounds for further optimization as inhibitors of the TRPM8 ion channel. Full article