A review on semi-aromatic polyamide TFC membranes prepared by interfacial polymerization: Potential for water treatment and desalination

Polyamide (PA) chemistry-based nanofiltration (NF) membranes have an important role in the field of seawater desalination and wastewater reclamation. Achieving an ultrathin and defect-free active layer via precisely controlled interfacial polymerization (IP) is an effective routine to improve the separation efficiencies of NF membranes. Herein, the morphologies and chemical structures of the thin-film composite (TFC) NF membranes were accurately regulated by tailoring the interfacial reaction temperature during the IP process. This strategy was achieved by controlling the temperature (-15, 5, 20, 35, and 50°) of the oil-phase solutions. The structural compositions, morphological variations, and separation features of the fabricated NF membranes were studied in detail. In addition, the formation mechanisms of the NF membranes featuring different PAs were also proposed and discussed. The temperature-assisted IP (TAIP) method greatly changed the compositions of the resultant PA membranes. A very smooth and thin PA film was obtained for the NF membranes fabricated at a low interfacial temperature; thus, a high 19.2 L m-2 h-1 bar-1 of water permeance and 97.7% of Na2SO4 rejection were observed. With regard to the NF membranes obtained at a high interfacial temperature, a lower water permeance and higher salt rejection with fewer membrane defects were achieved. Impressively, the high interfacial temperature-assisted NF membranes exhibited uniform coffee-ring-like surface morphologies. The special surface-featured NF membrane showed superior separation for selected heavy metals. Rejections of 93.9%, 97.9%, and 87.7% for Cu2+, Mn2+, and Cd2+ were observed with the optimized membrane. Three cycles of fouling tests indicated that NF membranes fabricated at low temperatures exhibited excellent antifouling behavior, whereas a high interface temperature contributed to the formation of NF membranes with high fouling tendency. This study provides an economical, facile, and universal TAIP strategy for tailoring the performances of TFC PA membranes for environmental water treatment.

Distinct impact of substrate hydrophilicity on performance and structure of TFC NF and RO polyamide membranes

Coupling activation and curing to tune the permselectivity of poly(piperazine amide) nanofiltration membranes

Removing salt from dye/salt mixtures using nanofiltration (NF) membranes needs to be improved to ensure high permeability, high selectivity, and antifouling performance. In this study, we used an interfacial polymerization (IP) technique to create a novel thin-film nanocomposite NF membrane by introducing two-dimensional MXene Ti3C2Tx into the polyamide (PA) layer. Enhanced IP reaction rate facilitated the overflow of residual solvent from the fresh PA layer's edge due to the MXene-mediated IP strategy, resulting considerable bubble-like nodules on the membrane surface. The unique nanostructure of PA effective layer could be tuned by controlling the MXene concentration in aqueous phase solution, which finally promoted the obtained membranes with superb permselectivity. In this way, the water permeability was elevated to a maximum value of 45.12 L m−1 h−1, nearly 1.58-fold compared to the PA-pristine membrane. Moreover, the Ti3C2Tx/NF membrane exhibited a superior dye/monovalent salt separation coefficient of 820, outperforming the pristine PA membrane and other NF membranes in the literature. Additionally, the MXene-assisted IP strategy designed an effective dye anti-fouling hydration layer, which played a crucial role in fouling resistance. This work illustrates a novel use of Ti3C2Tx to successfully regulate high-performance TFN PA membranes for potential application in dye/salt separation.

Membrane Filtration technique is being accepted worldwide as an environment friendly and energy efficient technique in Desalination Industry as compared to Thermal Desalination techniques. However, the performance of membranes which include permeate flux and rejection is affected by the membrane fouling. The properties of membrane and surface features such as porous structure, hydrophilicity/hydrophobicity charge, polymer characteristics, surface roughness determine the fouling potential of the membrane. The hydrophilic and smooth membrane surface is usually considered desirable in tackling membrane fouling issues. Therefore, many studies have focused on to enhance surface characteristics of membranes by surface coating with polymers and nanomaterials. Since, membrane coating is not done during fabrication of the most commercially available membranes, therefore, it is also important to determine the surface features of the commercially available membranes to investigate their membrane fouling potential. Thus, the objectives of this study were (1) to perform membrane surface characterization of commercial Reverse Osmosis (RO) and Nanofiltration (NF) membranes using techniques such as SEM, AFM, FTIR and XPS; (2) to measure hydrophilicity/hydrophobicity of commercial RO and NF membranes through water contact angle measurement using sessile drop method and (3) to measure the flux and percentage rejection of NF and RO membranes using Dead end filtration technique. Here, the characterization of membrane surface in terms of surface roughness, using SEM and AFM, showed that the commercial RO membrane had more ridge and valley structures and higher average surface roughness i.e. 71.24 nm as compared to NF membranes (6.63 nm). In addition, water contact angle measurements showed that the NF membrane was more hydrophilic as compared to RO membrane. The average contact angle found for RO membrane was 59.94°. On the other hand, it was observed that NF membrane is extremely hydrophilic in nature. Due to which, contact angle value was not obtained for most of the runs. The droplet could diffuse in less than 5 seconds. In addition, the dead-end filtration experiments showed that the RO membrane had much lower flux as compared to NF membrane. This can be associated with the pore structure of these membranes. Since, the NF membrane has porous structure, in oppose to RO membrane, the flux of the NF membrane is usually higher than the RO membranes. As the membrane surface roughness and hydrophobicity makes it more susceptible to the fouling leading to reduction in membrane flux and performance, it can be concluded from this study that there is a need for surface coating of RO membrane with suitable nanomaterials such as graphene oxide to improve its hydrophilicity and surface smoothness. This will eventually make the membrane more resistant to membrane fouling and will establish the use of membrane filtration technique in desalination industry in Qatar in the future. Microorganisms have been isolated from Gulf sea water, identified and differentiated and are being used to study the biofouling of RO and NF membranes, that would be coated to limit the fouling problems. Acknowledgement: This research was made possible by NPRP grant # [9-318-1-064] from the Qatar National Research Fund (a member of Qatar Foundation). The findings achieved herein are solely the responsibility of the author[s].

Interfacial polymerization technique has been widely employed to prepare reverse osmosis (RO) and nanofiltration (NF) membranes. The present study explores the possibility of preparing a polyamide membrane by interfacial polymerization and its utilization for the separation of CO2 and H2S from CH4. A novel ultraporous substrate of polysulfone (PSF) was prepared by phase inversion technique from a solution containing 18% PSF and 4% propionic acid in dimethyl formamide (DMF) solvent. Thin film composite (TFC) polyamide membrane was synthesized on PSF substrate from the reaction between meta-phenylene diamine in an aqueous media and isophthaloyl chloride in hexane. The membrane prepared was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) to study intermolecular interactions, crystallinity, thermal stability and surface morphology, respectively. Gas permeabilities of pure CO2, H2S, CH4, O2, and N2 gases were measured using the indigenously built permeation cell incorporated into a high-pressure gas separation manifold. At the feed pressure of 1 MPa, the membrane exhibited permeances of 15.2 GPU for CO2 and 51.6 GPU for H2S with selectivities of 14.4 and 49.1 for CO2/CH4 and H2S/CH4 systems, respectively. The observed N2 permeance of 0.95 GPU was close to that of CH4. The corresponding O2 permeance was 5.13 GPU with a reasonably high O2/N2 selectivity of 5.4. The effect of feed pressure on polyamide membrane performance was examined. Further, molecular dynamics (MD) simulations were employed to compute the cohesive energy density (CED), solubility parameter (δ) and sorption of CO2, H2S, CH4, O2, and N2 gases in polyamide membrane to corroborate theoretical study with experimentally determined gas transport properties.

Customized architecture and chemistry play a pivotal role in conferring exceptional permeability and selectivity to polyamide (PA) membranes for desalination and ionic separation. Herein, a new interfacial polymerization (IP) template, the ultrathin graphene oxide nanoribbon (GONR) networks, is developed to meet the need for minimizing the funnel effect and mediating the IP reaction toward a highly permeable and selective membrane. The coated GONR template efficiently represents the gutter layer role and regulates the adsorption and transport of amine monomers at the GONR interface, which is studied by molecular simulation as well. The structure, electrostatic interaction, capillary rise, and nanoconfinement of the IP template are manipulated by different GONR loadings to optimize the membrane structure. The optimized GONR loading at 0.02 g m−2 results in a hybrid layered GONR/PA‐thin‐film‐composite nanofiltration membrane with nanostrip crumpled structure beyond the PA context, ultrathin 15 nm PA nanofilm, 80% cross‐linking degree, and narrow pore size distribution. The membrane passes the upper bound trade‐off with a permeance of 21.3 L m−2 h−1 bar−1 and a remarkable rejection of 98% for Na2SO4. This research offers a fresh perspective on comprehensively understanding the role of the IP template in creating a desired membrane for efficient desalination and ionic separation.

In this paper, we review various novel/modified interfacial polymerization (IP) techniques for the fabrication of polyamide (PA) thin film composite (TFC)/thin film nanocomposite (TFN) membranes in both pressure-driven and osmotically driven separation processes. Although conventional IP technique is the dominant technology for the fabrication of commercial nanofiltration (NF) and reverse osmosis (RO) membranes, it is plagued with issues of low membrane permeability, relatively thick PA layer and susceptibility to fouling, which limit the performance. Over the past decade, we have seen a significant growth in scientific publications related to the novel/modified IP techniques used in fabricating advanced PA-TFC/TFN membranes for various water applications. Novel/modified IP lab-scale studies have consistently, so far, yielded promising results compared to membranes made by conventional IP technique, in terms of better filtration efficiency (increased permeability without compensating solute rejection), improved chemical properties (crosslinking degree), reduced surface roughness and the perfect embedment of nanomaterials within selective layers. Furthermore, several new IP techniques can precisely control the thickness of the PA layer at sub-10 nm and significantly reduce the usage of chemicals. Despite the substantial improvements, these novel IP approaches have downsides that hinder their extensive implementation both at the lab-scale and in manufacturing environments. Herein, this review offers valuable insights into the development of effective IP techniques in the fabrication of TFC/TFN membrane for enhanced water separation.

A nanofiltration membrane with positively and negatively charged groups by grafted p-aminosalicylic acid-Fe(III) chelation for Li+/Mg2+ efficient separation

Crumple-textured polyamide membranes via MXene nanosheet-regulated interfacial polymerization for enhanced nanofiltration performance

Aromatic polyamide (PA) membranes fabricated from interfacial polymerization are widely used for desalination and water treatment. The fabrication of the high-flux PA membrane requires a fundamental understanding of the molecular mechanisms of water dynamics in the PA, which is still obscure due to the limited experimental methods. Herein, molecular dynamics (MD) simulations were employed to establish an atomic model of ultrathin free-standing PA membranes with various thickness and to explore the thickness-dependent dynamics of water molecules in the PA membrane. Simulation results illustrate that the simulated PA membrane has an average pore radius of 3 Å similar to the free volume size of the experimental PA membrane measured by PALS. The PA could be identified as the swelling layer (SL) and the confined layer (CL) based on their water diffusion rates. The diffusivity of water in the confined layer of PA membrane was much lower than that in the swelling layer and thus determined the water flux of the PA membrane. The water diffusivity in the sub-8 nm PA membrane is greatly enhanced due to a very thin confined layer thickness, illustrating the mechanism of the experimentally fabricated sub-8 nm PA membrane having the dramatically enhanced water permeability. Furthermore, results show that water molecules tend to transport rapidly in the free space inside the PA membrane. Our results provide some insights into the thickness-dependent water dynamics in the PA on a molecular level and may help to design the next generation of high-flux PA membranes.

Preparation of nanocomposite aromatic polyamide reverse osmosis membranes by in-situ polymerization of bis(triethoxysilyl)ethane (BTESE)

A new optimized ultraviolet (UV) technique induced a photooxidation surface modification on thin-film composite (TFC) polyamide (PA) brackish water reverse osmosis (BWRO) membranes that improved membrane performance (i.e., permeability and organic fouling propensity). Commercial PA membranes were irradiated with UV-B light (285 nm), and the changes in the membrane performance were assessed through dead-end and cross-flow tests. UV-B irradiation at 12 J·cm-2 enhanced the pure water permeability by 34% in the dead-end tests without decreasing the mono- or divalent ion rejections, as compared with the pristine PA membrane, and led to less fouling by natural organic matter in the cross-flow tests. Scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) confirmed that UV-B irradiation opened the pore structure and created carboxylic and amine groups on the PA surface, leading to increased membrane surface charge and hydrophilicity. Thus, an optimal UV-B dose appears to modify only a thin layer of the PA membrane surface, which favorably enhances the membrane performance. UV-B did not alter the structure, flux, or salt rejection for cellulose triacetate (CTA)-based membranes. While other membrane surface modifications include oxidants, strong acids, and bases, the UV-B facile treatment is chemical-free, thus reducing chemical wastes, and easy to apply in roll-to-roll fabrication processes of PA membranes. The results also showed that a low UV irradiation dose could be applied to PA or CTA membranes for disinfection or photocatalytic oxidation.

Nanomorphogenesis of template-induced crumpled polyamide nanofiltration membranes

Effect of different manufacturing methods on polyamide reverse-osmosis membranes for desalination: Insights from molecular dynamics simulations