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Nanofiltration membranes produced with polyelectrolytes via the layer-by-layer technique are frequently researched, but misunderstood parameter is the polyelectrolyte concentration. Higher polyelectrolyte (PE) concentrations are known to produce thicker PE layers, but its effect on the membrane performance has only been studied in a limited fashion, leading to premature conclusions. In this work, two well-known strong polyelectrolytes, PDADMAC and PSS were used to prepare membranes using coating solutions with polyelectrolyte concentrations of 0.01, 0.1, 1.0, 2.5 and 5.0 wt% and two different salt concentrations in the coating solution of 0.05 and 1 M, as higher salt concentrations lead to thicker PE layers. The membrane performance of the prepared membranes is researched in terms of pure water permeability (PWP), molecular weight cut-off (MWCO) and the retention of different salts. In the first bilayer, membranes coated with a 0.05 M salt solution showed lower PWPs and MWCOs and higher salt retentions by increasing the PE concentration. After a certain number of coated bilayers, the MWCO and salt retentions reach a plateau for all PE concentrations; but the plateau value was obtained earlier by coating with a higher PE concentration. The membranes coated with the 1 M salt concentration had lower or comparable retention rates, except for MgCl2, than those coated with 0.05 M salt. The higher salt concentration resulted in more abundant PDADMAC in the membrane, which promotes the MgCl2 retentions for all bilayers. In conclusion, we found that the polyelectrolyte concentration significantly alters the membrane performance, but after coating 7 bilayers, the same size exclusion plateaus are reached.

Biomaterials often contain large quantities of water (50-98%), and with the current transition to a more biobased economy, drying these materials will become increasingly important. Contrary to the standard, thermodynamically inefficient chemical and thermal drying methods, dewatering by membrane separation will provide a sustainable and efficient alternative. However, biomaterials can easily foul membrane surfaces, which is detrimental to the performance of current membrane separations. Improving the antifouling properties of such membranes is a key challenge. Other recent research has been dedicated to enhancing the permeate flux and selectivity. In this review, we present a comprehensive overview of the design requirements for and recent advances in dewatering of biomaterials using membranes. These recent developments offer a viable solution to the challenges of fouling and suboptimal performances. We focus on two emerging development strategies, which are the use of electric-field-assisted dewatering and surface functionalizations, in particular with hydrogels. Our overview concludes with a critical mention of the remaining challenges and possible research directions within these subfields.

The gas separation performances of free-standing planar aligned nematic LC polymer films were investigated for gas separations of He, CO2, CH4 and Xe. The films consist of derivatives of 1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)s with respective cyano, chloro, methyl and phenyl substituents on the central aromatic cores. Two new LC derivatives of 1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)s were successfully synthesised and fully characterised. Single gas permeation and sorption data show increasing gas permeabilities with increasing steric size of the substituents while the ideal gas selectivity of He over CH4 and He over CO2 decreases. The sorption coefficient of all films is independent of the LC substituents, while the subsequently extracted diffusion coefficient for the films with a phenyl substituent is three times higher compared to the films with a cyano substituent, demonstrating that the steric size of the LC substituents mainly affects the diffusion of gasses rather than the solubility of the gases. Irrespective of a methyl or a phenyl substituent, a larger kinetic diameter of Xe gives a 20 times lower diffusion coefficient compared to the smaller species (CO2).

The flocculation of (co-)digested cattle and pig manure has rarely been investigated, leading to a rather intuitive use of flocculants in manure treatment processes, resulting in overdosing and increasing costs. Here, we investigate the effect of molecular weight, charge density and branching of reference and commercially available flocculants by establishing the optimal flocculant dosage and the corresponding maximum organic matter removal. Higher molecular weight flocculants show increased turbidity removal as result of their long chains corresponding to a higher amount adsorption sites. Results presented show that polymers with an increased cationic charge density give moderate and unstable flocculation due to the low amounts of non-charged parts essential for the hydrophobic interactions and hydrogen bonding. Further, the results show that a linear high molecular weight flocculant with a nonionic or a low anionic charge density is the most effective as it reached the highest organic matter removal at a low dosage.

Motivated by the need for efficient purification methods for the recovery of valuable resources, we developed a wire-electrospun membrane adsorber without the need for post-modification. The relationship between the fiber structure, functional-group density, and performance of electrospun sulfonated poly(ether ether ketone) (sPEEK) membrane adsorbers was explored. The sulfonate groups enable selective binding of lysozyme at neutral pH through electrostatic interactions. Our results show a dynamic lysozyme adsorption capacity of 59.3 mg/g at 10% breakthrough, which is independent of the flow velocity confirming dominant convective mass transport. Membrane adsorbers with three different fiber diameters (measured by SEM) were fabricated by altering the concentration of the polymer solution. The specific surface area as measured with BET and the dynamic adsorption capacity were minimally affected by variations in fiber diameter, offering membrane adsorbers with consistent performance. To study the effect of functional-group density, membrane adsorbers from sPEEK with different sulfonation degrees (52%, 62%, and 72%) were fabricated. Despite the increased functional-group density, the dynamic adsorption capacity did not increase accordingly. However, in all presented cases, at least a monolayer coverage was obtained, demonstrating ample functional groups available within the area occupied by a lysozyme molecule. Our study showcases a ready-to-use membrane adsorber for the recovery of positively charged molecules, using lysozyme as a model protein, with potential applications in removing heavy metals, dyes, and pharmaceutical components from process streams. Furthermore, this study highlights factors, such as fiber diameter and functional-group density, for optimizing the membrane adsorber's performance.

Porous electrodes govern the electrochemical performance and pumping requirements in redox flow batteries, yet conventional carbon-fiber-based porous electrodes have not been tailored to sustain the requirements of liquid-phase electrochemistry. 3D printing is an effective approach to manufacturing deterministic architectures, enabling the tuning of electrochemical performance and pressure drop. In this work, model grid structures are manufactured with stereolithography 3D printing followed by carbonization and tested as flow battery electrode materials. Microscopy, tomography, spectroscopy, fluid dynamics, and electrochemical diagnostics are employed to investigate the resulting electrode properties, mass transport, and pressure drop of ordered lattice structures. The influence of the printing direction, pillar geometry, and flow field type on the cell performance is investigated and mass transfer vs. electrode structure correlations are elucidated. It is found that the printing direction impacts the electrode performance through a change in morphology, resulting in enhanced performance for diagonally printed electrodes. Furthermore, mass transfer rates within the electrode are improved by helical or triangular pillar shapes or by using interdigitated flow field designs. This study shows the potential of stereolithography 3D printing to manufacture customized electrode scaffolds, which could enable multiscale structures with superior electrochemical performance and low pumping losses.

Low-cost cation exchange membranes with improved ionic conductivity and permselectivity are needed for the deployment of efficient large-scale energy storage technologies or separation technologies such as electrodialysis. In this work, a series of montmorillonite (Mt) clays and sulfonated poly(ether ether ketone) (SPEEK) composite membranes with 1 to 20 weight percentage (wt%) additives are studied. Two types of clays are investigated, a generic K30 Mt and an aluminum pillared (Al-pil) Mt with larger interlayer spacing owing to the inorganic crosslinks between the clay platelets. The addition of inorganic clays with two-dimensional geometries enables the formation of percolating sodium diffusing pathways with reduced tortuosity. As a result, the conductivity of the membranes increases with an increasing clay loading fraction, reaching up to 1.4 times that of the pure SPEEK with 20 wt% K30 Mt. The permselectivity of the native SPEEK membrane also improves with the addition of set amounts of K30 Mt, while the Al-pil Mt composites suffer from a slightly reduced permselectivity due to their higher water uptake. The voltaic efficiency of a concentration gradient flow battery shows that the addition of 20 wt% K30 Mt clay to the SPEEK polymer matrix can improve the voltaic efficiency by up to 10%.

Layer-by-layer (LbL) assembly of the alternating adsorption of oppositely charged polyions is an extensively studied method to produce nanofiltration membranes. In this work, the concept of chaotropicity of the polycation and its counterion is introduced in the LbL field. In general, the more chaotropic a polyion, the lower its effective charge, charge availability, and hydrophilicity. Here, this is researched for the well-known PDADMAC (polydiallyldimethylammonium chloride) and PAH (poly(allylamine) hydrochloride), and the synthesized PAMA (polyallylmultimethylammonium), with two different counterions (I- and Cl-). Higher chaotropicity (PDADMAC > PAMA-I > PAMA-Cl > PAH) translates into a reduced charge availability and a more pronounced extrinsic charge compensation, resulting in more mass adsorption and a higher pure water permeability. PAMA-containing membranes show the most interesting results in the series. Due to its molecular structure, the chaotropicity of this polycation perfectly lies between PDADMAC and PAH. Overall, the chaotropicity of PAMA membranes allows for the formation of the right balance between extrinsic and intrinsic charge compensation with PSS. Moreover, modifying the nature of the counterions of PAMA (I- or Cl-) allows to tune the density of the multilayer and results in lower size exclusion abilities with PAMA-I compared to PAMA-Cl (higher MWCO and lower MgSO4 retention). In general, the contextualization of the polyion interaction within the specific (poly)ion effects expands the understanding of the influence of the charge density of polycations without ignoring the chemical nature of the functional groups in their monomer units.

Forward osmosis (FO), using the osmotic pressure difference over a membrane to remove water, can treat highly foul streams and can reach high concentration factors. In this work, electrospun TFC membranes with a very porous open support (porosity: 82.3%; mean flow pore size: 2.9 µm), a dense PA-separating layer (thickness: 0.63 µm) covalently attached to the support and, at 0.29 g/L, having a very low specific reverse salt flux (4 to 12 times lower than commercial membranes) are developed, and their FO performance for the concentration of apple juice, manure and whey is evaluated. Apple juice is a low-fouling feed. Manure concentration fouls the membrane, but this results in only a small decrease in overall water flux. Whey concentration results in instantaneous, very severe fouling and flux decline (especially at high DS concentrations) due to protein salting-out effects in the boundary layer of the membrane, causing a high drag force resulting in lower water flux. For all streams, concentration factors of approximately two can be obtained, which is realistic for industrial applications.

The development of functionalized polyolefins for use as stimuli-responsive commodity polymers has recently received much attention. In this work, a microporous polypropylene (PP) scaffold is used to align and fortify a smectic liquid crystalline network (LCN) which can switch its gas permeability upon pH changes. The LCN is a photopolymerized liquid crystalline mixture of a dimerized benzoic acid derivative monoacrylate and a diacrylate crosslinker. In the hydrogen-bonded state, the composite membrane shows a high-molecular order and a low permeability for He, N2, and CO2 gases. By pH switching from the hydrogen-bonded state to the salt form, the molecular order is reduced, and the gas permeability is increased by one order of magnitude. This increase is mainly attributed to a loss in order of the system, increasing the free volume, resulting in an increased diffusibility. By exposing the composite film to basic or acidic environments, reversible switching between low and high gas permeability states is observed, respectively. The physical constraints imposed by the PP scaffold strengthens the membrane while the reversible switching inside the liquid crystalline polymer is maintained. This switching of gas permeation properties is not possible with the fragile freestanding LCN films alone.

Amorphous polymers are often used for gas separation but have a trade-off between gas permeability and selectivity. Here, the effect of chemical composition and temperature on gas permeability and solubility in well-ordered LC polymer membranes is investigated. Membranes with various compositions of a monomethacrylate LC (M1) with a crown ether functionality to enhance CO2 solubility and a smectic diacrylate (M2) cross-linker were fabricated, while all having the same order (smectic C) and alignment (planar). Single gas sorption and permeation data show for the membranes with 30 wt % M1 a higher CO2 solubility coefficient compared to membranes without M1, which results in a higher CO2 permeability and selectivity. For membranes that contain more than 30 wt % M1 decreasing layer spacings lead to reduced gas solubilities that result in lower gas permeabilities without additional selectivity gain toward CO2. The effect of temperature is demonstrated by comparing single gas sorption and permeation data below and above the Tg of the membranes. The diffusion coefficient increases above the Tg of the membranes with increasing M1 content leading to higher CO2 permeabilities and selectivities. These results show that not only the chemical composition but also the layer spacing of the smectic structures determines the gas separation performance of smectic LC polymer membranes.

The effect of layer spacing and halogenation on the gas separation performances of free-standing smectic LC polymer membranes is being investigated by molecular engineering. LC membranes with various layer spacings and halogenated LCs were fabricated while having a planar aligned smectic morphology. Single permeation and sorption data show a correlation between gas diffusion and layer spacing, which results in increasing gas permeabilities with increasing layer spacing while the ideal gas selectivity of He over CO2 or He over N2 decreases. The calculated diffusion coefficients show a 6-fold increase when going from membranes with a layer spacing of 31.9 Å to membranes with a layer spacing of 45.2 Å, demonstrating that the layer spacing in smectic LC membranes mainly affects the diffusion of gasses rather than their solubility. A comparison of gas sorption and permeation performances of smectic LC membranes with and without halogenated LCs shows only a limited effect of LC halogenation by a slight increase in both solubility and diffusion coefficients for the membranes with halogenated LCs, resulting in a slightly higher gas permeation and increased ideal gas selectivities towards CO2. These results show that layer spacing plays an important role in the gas separation performances of smectic LC polymer membranes.

To prevent greenhouse emissions into the atmosphere, separations like CO2/CH4 and CO2/N2 from natural gas, biogas, and flue gasses are crucial. Polymer membranes gained a key role in gas separations over the past decades, but these polymers are often not organized at a molecular level, which results in a trade-off between permeability and selectivity. In this work, the effect of molecular order and orientation in liquid crystals (LCs) polymer membranes for gas permeation is demonstrated. Using the self-assembly of polymerizable LCs to prepare membranes ensures control over the supramolecular organization and alignment of the building blocks at a molecular level. Robust freestanding LC membranes were fabricated that have various, distinct morphologies (isotropic, nematic cybotactic, and smectic C) and alignment (planar and homeotropic), while using the same chemical composition. Single gas permeation data show that the permeability decreases with increasing molecular order while the ideal gas selectivity of He and CO2 over N2 increases tremendously (36-fold for He/N2 and 21-fold for CO2/N2) when going from randomly ordered to the highly ordered smectic C morphology. The calculated diffusion coefficients showed a 10-fold decrease when going from randomly ordered membranes to ordered smectic C membranes. It is proposed that with increasing molecular order, the free volume elements in the membrane become smaller, which hinders gasses with larger kinetic diameters (Ar, N2) more than gasses with smaller kinetic diameters (He, CO2), inducing selectivity. Comparison of gas sorption and permeation performances of planar and homeotropic aligned smectic C membranes shows the effect of molecular orientation by a 3-fold decrease of the diffusion coefficient of homeotropic aligned smectic C membranes resulting in a diminished gas permeation and increased ideal gas selectivities. These results strongly highlight the importance of molecular order and orientation in LC polymer me

Forward osmosis (FO) is an emerging process to dewater whey streams energy efficiently. The driving force for the process is the concentration gradient between the feed (FS) and the concentrated draw (DS) solution. Here we investigate not only the effect of the DS concentration on the performance, but also that of the FS is varied to maintain equal driving force at different absolute concentrations. Experiments with clean water as feed reveal a flux increase at higher osmotic pressure. When high product purities and thus low reverse salt fluxes are required, operation at lower DS concentrations is preferred. Whey as FS induces severe initial flux decline due to instantaneous protein fouling of the membrane. This is mostly due to reversible fouling, and to a smaller extent to irreversible fouling. Concentration factors in the range of 1.2–1.3 are obtained. When 0.5 M NaCl is added to whey as FS, clearly lower fluxes are obtained due to more severe concentration polarization. Multiple runs over longer times show though that irreversible fouling is fully suppressed due to salting in/out effects and flux decline is the result of reversible fouling only.

Nanofiltration (NF) membrane processes are attractive to remove multivalent ions. As ion retention in NF membranes is determined by both size and charge exclusion, negatively charged membranes are required to reject negatively charged ions. Layer-by-layer assembly of alternating polycation (PC) and polyanion layers on top of a support is a versatile method to produce membranes. Especially the polyelectrolyte (PE) couple polydiallyldimethylammoniumchloride and poly(sodium-4-styrenesulfonate) (PDADMAC/PSS) is extensively investigated. This PE couple cannot form highly negatively charged membrane surfaces, due to interdiffusion and charge overcompensation of PDADMAC into the PSS layers, which limits the operational window to tailor membrane properties. We propose the use of asymmetric layer formation and show how combining two charge densities of one PC can produce negatively charged NF membranes. Starting from hollow fiber ultrafiltration supports coated with base layers of PDADMAC/PSS, they are coated with PDADMAC/PSS or poly(acrylamide-co-diallyldimethylammoniumchloride), P(AM-co-DADMAC)/PSS layers. P(AM-co-DADMAC) has a charge density of only 32% compared to 100% for PDADMAC. The particular novel membranes coated with P(AM-co-DADMAC) have a highly negatively charged surface and high permeabilities (7–19 L/[m2hbar]), with high retentions for Na2SO4 of up to 95%. These values position the developed membranes in the top range compared to commercial and other layer-by-layer membranes.

Reverse electrodialysis (RED) is an electro-membrane process to harvest renewable energy from salinity gradients. RED process models have been developed in the past, but they mostly assume that only NaCl is present in the feedwaters, which results in unrealistically high predictions. In the present work, an existing simple model is extended to accommodate the presence of magnesium ions and sulfate in the feedwaters, and potentially even more complex mixtures. All power loss mechanisms deriving from the presence of multivalent ions are included in the new model: increased membrane electrical resistance, uphill transport of multivalent ions from the river to the seawater compartment, and membrane permselectivity loss. This new model is validated with experimental and literature data of membrane electrical resistance (at 10 mol. % MgCl2 for the CEMs and 25 mol. % Na2SO4 for the AEMs), RED stack performance (up to 50 mol. % MgCl2 or Na2SO4 in the feedwaters), and ion transport (at 10 mol. % MgCl2 or Na2SO4 in the feedwaters) showing very good agreement between model predictions and experimental data. Finally, we showed that the developed model not only describes experimental data but can also predict RED performances under a variety of conditions and cross-flow configurations (single-stage with and without electrode segmentation, multi-stage in co-current and counter-current mode) and feedwater compositions (only NaCl, with Na2SO4, with MgCl2, and with MgSO4). It thus provides a very valuable tool to design and evaluate RED process systems.

Water vapor permeation under supercritical carbon dioxide (scCO2) conditions through dense polydimethylsiloxane (PDMS) was investigated up to pressure of 185 bars to evaluate the regenerability of scCO2 as desiccant to dehydrate fresh products that are prone to product deterioration during conventional drying. This study experimentally examined the impact of concentration polarization on the H2O vapor permeation through dense PDMS membranes in the presence of sub- and supercritical CO2. The results were compared to a system containing N2 instead of CO2. For the CO2 system, the residual mass transfer resistance, which excludes the membrane layer resistance, decreased down to zero with increasing feed pressure, at 90 bar. This is the result of the convergence of the H2O contents of the feed bulk and permeate, which leads to a change of the main H2O transport mechanism within the feed boundary layer from diffusion to convection. Here the H2O and CO2 molecules are transported with comparable speed towards the membrane surface. For the system with N2, the opposite trend was found, due to the maintained significant difference in transport speed between H2O and N2 even at elevated pressures. Consequently, the water vapor transport rate through the PDMS membrane is governed by the type of matrix fluid (CO2 or N2).

Supercritical CO 2 (scCO 2 ), used in the food industry as a water extraction agent, requires dehydration units for regeneration. The present study assesses the economics of membrane-based dehydration of scCO 2 . In contrast to earlier studies, the contribution, next to the membrane, also the contributions of the mass transfer resistances of the feed and permeate boundary are included, which have a dominant effect on the final process design and economics. In addition, our work also extrapolates the process to industrial scale evaluating different configurations and process conditions. Specifically, the contribution of the membrane and membrane unit costs is discussed in more detail. Including the mass transfer resistances of feed and permeate boundary layer reduces the water flux across the membrane up to a factor 150, implying a larger required membrane surface area for a given water removal rate, and thus higher costs. Using a SPEEK-based membrane, the total drying costs, normalized for the amount of water removed, minimize around a skin layer thickness of 1 μm, i.e., not too thin to permeate and thus spill too much CO 2 and not too thick to hamper the H 2 O flux. Because the feed boundary layer dominates water transport, conditions that minimize its thickness reduce total costs. A reduction of the feed boundary layer dominance can be achieved by adjusting channel height, cross-flow velocity and the density and viscosity of scCO 2 , the latter two by increasing the operational temperature from 45 to 65 °C (at 130 bar). Compared to the benchmark zeolite process currently available, the membrane-based process for drying scCO 2 outlined and optimized in the present study results in a 50% saving of total drying costs. These savings can be achieved by using a dense polymeric membrane with a H 2 O permeability of at least 10,000 Barrer and a CO 2 permeability of at mo

When harvesting salinity gradient energy via reverse electrodialysis (RED), stack performance is monitored using DC characterizations, which does not provide information about the nature and mechanisms underlying fouling inside the stack. In order to assess the potential of natural salinity gradients as renewable energy source, progress in the fields of fouling monitoring and controlling is vital. To improve fouling and cleaning monitoring, experiments with sodium dodecylbenzenesulfonate (SDBS) were carried out while at the same time the electrochemical impedance spectroscopy (EIS) was measured at the RED stack level. EIS showed how SDBS affected the ohmic resistance of the stack, the non-ohmic resistance of the AEM and the non-ohmic resistance of the CEM on different time scales. Such detailed investigation into the effect of SDBS on different stack elements offered by EIS is not possible with traditional DC characterization. The results presented in this work illustrate the potential of EIS at the stack level for fouling monitoring. The knowledge presented shows the possibility to include EIS in up-scaled natural salinity gradient RED applications for fouling monitoring purposes.

Continuous drying processes using supercritical CO2 (scCO2) as a water extraction agent require 24/7 operational dehydration units for scCO2 regeneration. Dehydration units using dense polymeric membranes are considered a cost effective, sustainable alternative to the current zeolite-based units. The focus of previous studies on the membrane-based dehydration of scCO2 was always on the membrane itself whereas boundary layer effects, e.g., concentration polarization, were not taken into account. To quantify the boundary layer effects, simulations were performed using three different membrane materials: SPEEK, Nafion® 117, and PEBAX® 1074. Process conditions during the simulations ranged from 8.0 to 18.0 MPa and 40 to 100 °C. Even though the three types of membranes examined differ in their H2O permeability and H2O over CO2 selectivity, in all cases 80% of the total mass-transfer resistance can be assigned to concentration polarization effects, making it the dominant parameter for water transport. Despite high but differing intrinsic water permeabilities of all three membranes materials, the H2O transport, thus H2O flux through the membrane is significantly reduced by concentration polarization down to similar levels. This makes it necessary to use larger membrane areas, that result in higher CO2 fluxes. As a consequence, material selection is predominantly based on the ability to reject CO2. Optimization of process conditions other than membrane material is briefly discussed.

The fabrication of a cationic nanoporous smectic liquid crystal network (LCN) based on hydrogen bonded heterodimers is presented. The method relies on a supramolecular complex made from a pyridyl bearing reactive mesogen hydrogen bonded to a non-reactive benzoic acid template. Upon addition of a cross-linker, a smectic liquid crystalline phase is obtained that can be fixed by photopolymerization. It was found that the lamellar structure was maintained after template removal when 25 wt% or more cross-linker was used, yielding a nanoporous LCN. After H3PO4 immobilization in the pores of the LCN, a cationic 2D nanoporous polymer is obtained showing high and anisotropic anhydrous proton conductivity.