Membranes — Open Access Journal of Membrane Technology

This paper reviews the membrane processes for the nuclear fusion fuel cycle—namely, the treatment of the plasma exhaust gases and the extraction of tritium from the breeding blankets. With respect to the traditional processes, the application of membrane reactors to the fusion fuel cycle reduces the tritium inventory and processing time, thus increasing the safety and availability of the system. As an example, self-supported Pd-alloy membrane tubes have been studied for the separation of hydrogen and its isotopes from both gas- and liquid-tritiated streams through water-gas shift and isotopic swamping reactions. Furthermore, this paper describes an innovative membrane system (Membrane Gas–Liquid Contactor) for the extraction of hydrogen isotopes from liquid LiPb blankets. Porous membranes are exposed to the liquid metal that penetrates the pores without passing through them, then realizing a gas–liquid interface through which the mass transfer of hydrogen isotopes takes place. Compared to the conventional hydrogen isotope extraction processes from LiPb that use the “permeator against vacuum” concept, the proposed process significantly reduces mass-transfer resistance by improving the efficiency of the tritium recovery system. Full article

Surface wettability-tailored porous ceramic/metallic membranes (in the tubular and planar disc form) were prepared and studied for both vapor-phase separation and liquid pervaporative separations of water-ethanol mixtures. Superhydrophobic nanoceramic membranes demonstrated more selective permeation of ethanol (relative to water) by cross-flow pervaporation of liquid ethanol–water mixture (10 wt % ethanol feed at 80 °C). In addition, both superhydrophilic and superhydrophobic membranes were tested for the vapor-phase separations of water–ethanol mixtures. Porous inorganic membranes having relatively large nanopores (up to 8-nm) demonstrated good separation selectivity with higher permeation flux through a non-molecular-sieving mechanism. Due to surface-enhanced separation selectivity, larger nanopore-sized membranes (~5–100 nm) can be employed for both pervaporation and vapor phase separations to obtain higher selectivity (e.g., permselectivity for ethanol of 13.9 during pervaporation and a vapor phase separation factor of 1.6), with higher flux due to larger nanopores than the traditional size-exclusion membranes (e.g., inorganic zeolite-based membranes having sub-nanometer pores). The prepared superhydrophobic porous inorganic membranes in this work showed good thermal stability (i.e., the large contact angle remains the same after 300 °C for 4 h) and chemical stability to ethanol, while the silica-textured superhydrophilic surfaced membranes can tolerate even higher temperatures. These surface-engineered metallic/ceramic nanoporous membranes should have better high-temperature tolerance for hot vapor processing than those reported for polymeric membranes. Full article

Lactic acid (LA) was produced on a pilot scale using a defined medium with glucose, acid whey, sugar bread and crust bread. The fermentation broths were then subjected to micro- and nanofiltration. Microfiltration efficiently separated the microbial cells. The highest average permeate flow flux was achieved for the defined medium (263.3 L/m²/h) and the lowest for the crust bread-based medium (103.8 L/m²/h). No LA losses were observed during microfiltration of the acid whey, whilst the highest retention of LA was 21.5% for crust bread. Nanofiltration led to high rejections of residual sugars, proteins and ions (sulphate, magnesium, calcium), with a low retention of LA. Unconverted sugar rejections were 100% and 63% for crust bread and sugar bread media respectively, with corresponding LA losses of 22.4% and 2.5%. The membrane retained more than 50% of the ions and proteins present in all media and more than 60% of phosphorus. The average flux was highly affected by the nature of the medium as well as by the final concentration of LA and sugars. The results of this study indicate that micro- and nanofiltration could be industrially employed as primary separation steps for the biotechnologically produced LA. Full article

The efficient separation of gases has industrial, economic, and environmental importance. Here, we report the improvement in gas separation performance of a polyimide-based matrix (Matrimid^®5218) filled with a Cu-based metal organic framework [MOF, Cu₃(BTC)₂] with two different ionic liquids (ILs) confined within the pores. The chosen ILs are commonly used in gas solubilization, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF₄]) and 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][OTf]), and the incorporation of the [EMIM][BF₄]@Cu-BTC and [EMIM][OTf]@Cu-BTC composites in Matrimid^®5218 proved to be an efficient strategy to improve the permeability and selectivity toward CO₂/N₂ and CO₂/CH₄ mixtures. Full article

Sputtered Pd77%Ag23% membranes of thickness 2.2–8.5 µm were subjected to a three-step heat treatment in air (HTA) to investigate the relation between thickness and the reported beneficial effects of HTA on hydrogen transport. The permeability experiments were complimented by volumetric hydrogen sorption measurements and atomic force microscopy (AFM) imaging in order to relate the observed effects to changes in hydrogen solubility and/or structure. The results show that the HTA—essentially an oxidation-reduction cycle—mainly affects the thinner membranes, with the hydrogen flux increasing stepwise upon HTA of each membrane side. The hydrogen solubility is found to remain constant upon HTA, and the change must therefore be attributed to improved transport kinetics. The HTA procedure appears to shift the transition from the surface to bulk-limited transport to lower thickness, roughly from ~5 to ≤2.2 µm under the conditions applied here. Although the surface topography results indicate that HTA influences the surface roughness and increases the effective membrane surface area, this cannot be the sole explanation for the observed hydrogen flux increase. This is because considerable surface roughening occurs during hydrogen permeation (no HTA) as well, but not accompanied by the same hydrogen flux enhancement. The latter effect is particularly pronounced for thinner membranes, implying that the structural changes may be dependent on the magnitude of the hydrogen flux. Full article

The pulp and paper industry is one of the most important industrial sectors worldwide, and has considerable potential for the sustainable fractionation of lignocellulosic biomass to provide valuable compounds. Ultrafiltration (UF) is a suitable separation technique for the profitable production of hemicelluloses from process water from thermomechanical pulping (ThMP), but is limited by membrane fouling. Improvements in cleaning protocols and new alternative cleaning agents are required to ensure a long membrane lifetime, and thus a sustainable process. This study, therefore, focuses on the cleaning of polymeric UF membranes after the filtration of ThMP process water, comparing alkaline with enzymatic cleaning agents. The aim was to develop a cleaning procedure that is efficient under mild conditions, resulting in a lower environmental impact. It was not possible to restore the initial permeability of the membrane when cleaning the membrane with enzymes alone, but the permeability was restored when using a two-step cleaning process with enzymes in the first step and an alkaline cleaning agent in the second step. Scanning electron microscopy gave a deeper inside into the cleaning efficiency. Attenuated total reflectance Fourier-transform infrared spectroscopy analysis confirmed that not only polysaccharides, but also extractives are adsorbed onto the membrane surface. Full article

Pressure-dependent breakthrough of nanobioparticles in filtration was observed and it was related to depend on both convective forces due to flow and diffusion as a result of Brownian motion. The aim of this work was to investigate the significance of Brownian motion on nanoparticle and virus capture in a nanocellulose-based virus removal filter paper through theoretical modeling and filtration experiments. Local flow velocities in the pores of the filter paper were modeled through two different approaches (i.e., with the Hagen–Poiseuille equation) and by evaluating the superficial linear flow velocity through the filter. Simulations by solving the Langevin equation for 5 nm gold particles and 28 nm ΦX174 bacteriophages showed that hydrodynamic constraint is favored for larger particles. Filtration of gold nanoparticles showed no difference in retention for the investigated fluxes, as predicted by the modeling of local flow velocities. Filtration of ΦX174 bacteriophages exhibited a higher retention at higher filtration pressure, which was predicted to some extent by the Hagen–Poiseuille equation but not by evaluation of the superficial linear velocity. In all, the hydrodynamic theory was shown able to explain some of the observations during filtration. Full article

To improve the filtration performance and properties of organic solvent nanofiltration (OSN) membranes, we firstly introduce nanoporous silica (SiO₂) particles into the polyamide (PA) active layer of polysulfone (PSf) membrane via an interfacial polymerization process. Results from the study revealed that introduction of SiO₂ influenced the properties of PSf/PA-SiO₂ composite membranes by changing the surface roughness and hydrophilicity. Moreover, results also indicated that nanoporous SiO₂ modified membranes showed an improved performance of alcohols solvent permeance. The PSf/PA-SiO₂ composite membrane modified by 0.025 wt % of SiO₂ reached a permeance of 3.29 L m⁻² h⁻¹ bar⁻¹ for methanol and 0.42 L m⁻² h⁻¹ bar⁻¹ for ethanol, which were 20.0% and 13.5% higher than the control PSf membrane (permeance of 2.74 L m⁻² h⁻¹ bar⁻¹ for methanol and 0.37 L m⁻² h⁻¹ bar⁻¹ for ethanol). Conclusively, we demonstrated that the increase of membrane hydrophilicity and roughness were major factors contributing to the improved alcohols solvent permeance of the membranes. Full article

A supported liquid membrane-hollow fiber system (HFSLM) has been developed to determine zinc speciation in aquatic environments. The liquid membrane consisted of an organic solution of bis-(2-ethylhexyl)phosphoric acid (D2EHPA) impregnated in the microporous of a polypropylene hollow fiber. The membrane contacted both the donor solution, that contained the metal and the stripping solution, placed in the lumen of the hollow fiber, where the metal was preconcentrated. Different parameters affecting the Zn²⁺ transport efficiency have been evaluated such as the composition of both the donor and stripping solutions as well as the membrane phase. Extraction and transport efficiencies of free Zn(II) higher than 90% were obtained with a liquid membrane consisting of a 0.1 M D2EHPA solution in dodecane and a 0.1 M HNO₃ solution as the stripping phase. The developed HFSLM was used to study the effect of different ligands (EDTA and citric acid) in the donor phase of Zn(II) transport and to investigate the selectivity of the membrane towards Zn when other metals were also present. Finally, the HFSLM system was successfully applied to estimate the free Zn(II) concentrations in three water samples from a mining area. Moreover, the HFSLM system facilitates the analytical determination of trace Zn(II) levels allowing the achievement of enrichment factors of around 700 in the stripping phase. Full article

Supported cellulose ultrafiltration membranes are cast from a cellulose-ionic liquid solution by the immersion precipitation technique. The effects of coagulation bath temperature and polymer concentration in the casting solution on the membrane morphology, wettability, pure water flux, molecular weight cut-off, and fouling resistance are studied. Scanning electron microscopy, contact angle measurements, atomic force microscopy, and filtration experiments are carried out in order to characterise the obtained ultrafiltration cellulose membranes. The results show the effect of coagulation bath temperature and polymer concentration on the surface morphology and properties of cellulose ultrafiltration membranes. Optimisation of the two parameters leads to the creation of dense membranes with good pure water fluxes and proven fouling resistance towards humic acid water solutions. Full article

Oily wastewater discharge from various industry processes and activities have caused dramatic impacts on the human and environment. Treatment of oily wastewater using membrane technology has gained worldwide attention due to its efficiency in removing the amount and concentration of oil and grease as well as other specific pollutants in order to be reused or to fulfill stringent discharge standard. The application of thin film composite (TFC) membrane in reverse osmosis (RO) and forward osmosis (FO) for oily wastewater treatment is an emerging and exciting alternative in this field. This review presents the recent and distinctive development of TFC membranes to address the issues related to oily wastewater treatment. The recent advances in terms of TFC membrane design and separation performance evaluation are reviewed. This article aims to provide useful information and strategies, in both scientific knowledge advancement and practical implementation point of view, for the application TFC membrane for oily wastewater treatment. Full article

Controlling surface–protein interaction during wastewater treatment is the key motivation for developing functionally modified membranes. A new biocatalytic thermo-responsive poly vinylidene fluoride (PVDF)/nylon-6,6/poly(N-isopropylacrylamide)(PNIPAAm) ultrafiltration membrane was fabricated to achieve dual functionality of protein-digestion and thermo-responsive self-cleaning. The PVDF/nylon-6,6/PNIPAAm composite membranes were constructed by integrating a hydrophobic PVDF cast layer and hydrophilic nylon-6,6/PNIPAAm nanofiber layer on to which trypsin was covalently immobilized. The enzyme immobilization density on the membrane surface decreased with increasing PNIPAAm concentration, due to the decreased number of amine functional sites. An ultrafiltration study was performed using the synthetic model solution containing BSA/NaCl/CaCl_2, where the PNIPAAm containing biocatalytic membranes demonstrated a combined effect of enzymatic and thermo-switchable self-cleaning. The membrane without PNIPAAm revealed superior fouling resistance and self-cleaning with an R_PD of 22%, compared to membranes with 2 and 4 wt % PNIPAAm with 26% and 33% R_PD, respectively, after an intermediate temperature cleaning at 50 °C, indicating that higher enzyme density offers more efficient self-cleaning than the combined effect of enzyme and PNIPAAm at low concentration. The conformational volume phase transition of PNIPAAm did not affect the stability of immobilized trypsin on membrane surfaces. Such novel surface engineering design offer a promising route to mitigate surface–protein contamination in wastewater applications. Full article

The use of the Nernst–Planck and Poisson (NPP) equations allows computation of the space charge density near solution/electrode or solution/ion-exchange membrane interface. This is important in modelling ion transfer, especially when taking into account electroconvective transport. The most solutions in literature use the condition setting a potential difference in the system (potentiostatic or potentiodynamic mode). However, very often in practice and experiment (such as chronopotentiometry and voltammetry), the galvanostatic/galvanodynamic mode is applied. In this study, a depleted stagnant diffusion layer adjacent to an ion-exchange membrane is considered. In this article, a new boundary condition is proposed, which sets a total current density, i, via an equation expressing the potential gradient as an explicit function of i. The numerical solution of the problem is compared with an approximate solution, which is obtained by a combination of numerical solution in one part of the diffusion layer (including the electroneutral region and the extended space charge region, zone (I) with an analytical solution in the other part (the quasi-equilibrium electric double layer (EDL), zone (II). It is shown that this approach (called the “zonal” model) allows reducing the computational complexity of the problem tens of times without significant loss of accuracy. An additional simplification is introduced by neglecting the thickness of the quasi-equilibrium EDL in comparison to the diffusion layer thickness (the “simplified” model). For the first time, the distributions of concentrations, space charge density and current density along the distance to an ion-exchange membrane surface are computed as functions of time in galvanostatic mode. The calculation of the transition time, τ, for an ion-exchange membrane agree with an experiment from literature. It is suggested that rapid changes of space charge density, and current density with time and distance, could lead to lateral electroosmotic flows delaying depletion of near-surface solution and increasing τ. Full article

Porous metal membranes have recently received increasing attention, and significant progress has been made in their preparation and characterisation. This progress has stimulated research in their applications in a number of key industries including wastewater treatment, dairy processing, wineries, and biofuel purification. This review examines recent significant progress in porous metal membranes including novel fabrication concepts and applications that have been reported in open literature or obtained in our laboratories. The advantages and disadvantages of the different membrane fabrication methods were presented in light of improving the properties of current membrane materials for targeted applications. Sintering of particles is one of the main approaches that has been used for the fabrication of commercial porous metal membranes, and it has great advantages for the fabrication of hollow fibre metal membranes. However, sintering processes usually result in large pores (e.g., >1 µm). So far, porous metal membranes have been mainly used for the filtration of liquids to remove the solid particles. For porous metal membranes to be more widely used across a number of separation applications, particularly for water applications, further work needs to focus on the development of smaller pore (e.g., sub-micron) metal membranes and the significant reduction of capital and maintenance costs. Full article

In this paper, an overview on thermodynamic aspects related to hydrogen-metal systems in non-ideal conditions is provided, aiming at systematically merging and analyzing information achieved from several different studies present in the open literature. In particular, the relationships among inner morphology, dissolved hydrogen and internal stresses are discussed in detail, putting in evidence the conformation complexity and the various types of dislocations induced by the presence of H-atoms in the lattice. Specifically, it is highlighted that the octahedral sites are preferentially occupied in the FCC metals (such as palladium), whereas tetrahedral sites are more energetically favored in BCC-structured ones (such as vanadium). These characteristics are shown to lead to a different macroscopic behavior of the two classes of metals, especially in terms of solubility and mechanical failure due to the consequent induced stresses. Furthermore, starting from the expression of the chemical potential generally presented in the literature, a new convenient expression of the activity of the H-atoms dissolved into the metal lattice as a function of the H-concentration is achieved. Such an activity expression is then used in the dissolution equilibrium relationship, which is shown to be the overall result of two different phenomena: (i) dissociative adsorption of molecular hydrogen onto the surface; and (ii) atomic hydrogen dissolution from the surface to the metal bulk. In this way, the obtained expression for equilibrium allows a method to calculate the equilibrium composition in non-ideal conditions (high pressure), which are of interest for real industrial applications. Full article

Dense metal membranes that are based on palladium (Pd) are promising for hydrogen separation and production due to their high selectivity and permeability. Optimization of alloy composition has normally focused on bulk properties, but there is growing evidence that grain boundaries (GBs) play a crucial role in the overall performance of membranes. The present study provides parameters and analyses of GBs in the ternary Pd-Ag-Cu system, based on first-principles electronic structure calculations. The segregation tendency of Cu, Ag, and vacancies towards 12 different coherent ∑ GBs in Pd was quantified using three different procedures for relaxation of supercell lattice constants, representing the outer bounds of infinitely elastic and stiff lattice around the GBs. This demonstrated a clear linear correlation between the excess volume and the GB energy when volume relaxation was allowed for. The point defects were attracted by most of the GBs that were investigated. Realistic atomic-scale models of binary Pd-Cu and ternary Pd-Cu-Ag alloys were created for the ∑5(210) boundary, in which the strong GB segregation tendency was affirmed. This is a starting point for more targeted engineering of alloys and grain structure in dense metal membranes and related systems. Full article

Enhancement of membrane permeability at no detriment of its other performances, e.g., selectivity, is a goal-directed objective in membrane fabrication. A novel antioxidant DES-lignin (lignin extracted from birch wood by using a deep eutectic solvent) polyethersulfone (PES) membrane, containing 0–1 wt % DES-lignin, was fabricated with the phase inversion technique. The performance and morphology of the fabricated membranes were characterized by a pure water flux, polyethylene glycol (PEG) retention, Fourier transform infrared spectroscopy, scanning electron microscopy, and contact angle measurements. Membranes with less negative charge and better hydrophilicity were obtained when the DES-lignin content in the polymer solution was increased. With the highest dosage, the incorporation of DES-lignin in the membrane matrix improved the membrane permeability by 29.4% compared to a pure PES membrane. Moreover, no leakage of DES-lignin from the membrane structure was observed, indicating good compatibility of DES-lignin with the PES structure. It was also found that the improvement of both rejection and pure water flux could be achieved by using a small dosage of DES-lignin (0.25 wt %) in membrane fabrication. The membranes incorporated with DES-lignin showed higher DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2-Azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)) scavenging activity compared to the pure membrane, where 2.6 and 1.1 times higher DPPH and ABTS scavenging activity was observed with the highest DES-lignin content (1 wt %). Thus, the results of this study demonstrate well the feasibility of utilizing DES-lignin as an antioxidant bio-based hydrophilicity promoter in the fabrication of ultrafiltration membranes. Full article

Phosphorene is a two-dimensional material exfoliated from bulk phosphorus and it possesses a band gap. Specifically, relevant to the field of membrane science, the band gap of phosphorene provides it with potential photocatalytic properties, which could be explored in making reactive membranes that can self-clean. The goal of this study was to develop an innovative and robust membrane that is able to control and reverse fouling with minimal changes in membrane performance. To this end, for the first time, membranes have been embedded with phosphorene. Membrane modification was verified by the presence of phosphorus on membranes, along with changes in surface charge, average pore size, and hydrophobicity. After modification, phosphorene-modified membranes were used to filter methylene blue (MB) under intermittent ultraviolet light irradiation. Phosphorene-modified and unmodified membranes displayed similar rejection of MB; however, after reverse-flow filtration was performed to mimic pure water cleaning, the average recovered flux of phosphorene-modified membranes was four times higher than that of unmodified membranes. Furthermore, coverage of MB on phosphorene membranes after reverse-flow filtration was four times lower than that of unmodified membranes, which supports the hypothesis that phosphorene membranes operated under intermittent ultraviolet irradiation can become self-cleaning. Full article

A predictive model correlating the parameters in the mass transfer-based model Spiegler–Kedem to the pure water permeability is presented in this research, which helps to select porous polyamide membranes for enhanced oil recovery (EOR) applications. Using the experimentally obtained values of flux and rejection, the reflection coefficient σ and solute permeability P_s have been estimated as the mass transfer-based model parameters for individual ions in seawater. The reflection coefficient and solute permeability determined were correlated with the pure water permeability of a membrane, which is related to the structural parameters of a membrane. The novelty of this research is the development of a model that consolidates the various complex mechanisms in the mass transfer of ions through the membrane to an empirical correlation for a given feed concentration and membrane type. These correlations were later used to predict ion rejections of any polyamide membrane with a known pure water permeability and flux with seawater as a feed that aids in the selection of suitable nanofiltration (NF) for smart water production. Full article