Correlating PSf Support Physicochemical Properties with the Formation of Piperazine-Based Polyamide and Evaluating the Resultant Nanofiltration Membrane Performance.
ABSTRACT: Membrane support properties influence the performance of thin-film composite nanofiltration membranes. We fabricated several polysulfone (PSf) supports. The physicochemical properties of PSf were altered by adding polyethylene glycol (PEG) of varying molecular weights (200⁻35,000 g/mol). This alteration facilitated the formation of a thin polyamide layer on the PSf surface during the interfacial polymerization reaction involving an aqueous solution of piperazine containing 4-aminobenzoic acid and an organic solution of trimesoyl chloride. Attenuated total reflectance-Fourier transform infrared validated the presence of PEG in the membrane support. Scanning electron microscopy and atomic force microscopy illustrated that the thin-film polyamide layer morphology transformed from a rough to a smooth surface. A cross-flow filtration test indicated that a thin-film composite polyamide membrane comprising a PSf support (TFC-PEG20k) with a low surface porosity, small pore size, and suitable hydrophilicity delivered the highest water flux and separation efficiency (J = 81.1 ± 6.4 L·m-2·h-1, RNa2SO4 = 91.1% ± 1.8%, and RNaCl = 35.7% ± 3.1% at 0.60 MPa). This membrane had a molecular weight cutoff of 292 g/mol and also a high rejection for negatively charged dyes. Therefore, a PSf support exhibiting suitable physicochemical properties endowed a thin-film composite polyamide membrane with high performance.
Project description:In this study, modification of polysulfone (PSf)/sulfonated polysulfone (SPSf) blended porous ultrafiltration (UF) support membranes was proposed to improve the reverse osmosis (RO) performance of aromatic polyamide thin film composite (TFC) membranes. The synergistic effects of solvent, polymer concentration, and SPSf doping content in the casting solution were investigated systematically on the properties of both porous supports and RO membranes. SEM and AFM were combined to characterize the physical properties of the membranes, including surface pore natures (porosity, mean pore radius), surface morphology, and section structure. A contact angle meter was used to analyze the membrane surface hydrophilicity. Permeate experiments were carried out to evaluate the separation performances of the membranes. The results showed that the PSf/SPSf blended porous support modified with 6 wt % SPSf in the presence of DMF and 14 wt % PSf had higher porosity, bigger pore diameter, and a rougher and more hydrophilic surface, which was more beneficial for fabrication of a polyamide TFC membrane with favorable reverse osmosis performance. This modified PSf/SPSf support endowed the RO membrane with a more hydrophilic surface, higher water flux (about 1.2 times), as well as a slight increase in salt rejection than the nascent PSf support. In a word, this work provides a new facile method to improve the separation performance of polyamide TFC RO membranes via the modification of conventional PSf porous support with SPSf.
Project description:Polyamide-based thin-film composite nanofiltration membranes are widely used for potable water decontamination, brackish water desalination and wastewater reutilization. However, enhancing the water permeance of the polyamide layer within the thin-film composite nanofiltration membrane still remains a great challenge, because of the relatively large thickness and high transport resistance of the polyamide layer produced by intractable interfacial polymerization. Herein, we reported a two-in-one strategy to prepare ultra-permeable nanofiltration membranes via covalent organic framework (COF) nanofiber scaffold mediated interfacial polymerization. The highly porous and hydrophilic COF nanofiber scaffolds enhanced the controlled release of amine monomers, leading to ultrathin polyamide layers. Also, the relatively smooth COF nanofiber scaffolds can be spontaneously evolved into rugged and uneven architectures during interfacial polymerization, providing rough substrates for enlarging the actual areas of polyamide layers. Therefore, the increased areas of polyamide layers were employed as additional water permeable domains. Arising from the synergetic effect of the ultrathin and increased water permeation domains, the produced membranes exhibit exceptional nanofiltration performance with a water permeance of up to 31.1 L m–2 h–1 bar–1 and a Na2SO4 rejection rate of about 95%, outperforming most other nanofiltration membranes. This highly accessible technique opens a new avenue for the design and engineering of ultra-permeable thin-film composite nanofiltration membranes, highlighting its great potential in providing clean water.
Project description:A membrane with both high ion conductivity and selectivity is critical to high power density and low-cost flow batteries, which are of great importance for the wide application of renewable energies. The trade-off between ion selectivity and conductivity is a bottleneck of ion conductive membranes. In this paper, a thin-film composite membrane with ultrathin polyamide selective layer is found to break the trade-off between ion selectivity and conductivity, and dramatically improve the power density of a flow battery. As a result, a vanadium flow battery with a thin-film composite membrane achieves energy efficiency higher than 80% at a current density of 260?mA?cm<sup>-2</sup>, which is the highest ever reported to the best of our knowledge. Combining experiments and theoretical calculation, we propose that the high performance is attributed to the proton transfer via Grotthuss mechanism and Vehicle mechanism in sub-1 nm pores of the ultrathin polyamide selective layer.
Project description:This paper focus to examine the best molecular interaction between Polyamide Thin Film Composite (PA TFC) layers with different properties of the support membrane. The support membrane of Nylon 66 (N66) and Polyvinylidene fluoride (PVDF) was chosen to represent the hydrophilic and hydrophobic model respectively in the Molecular Dynamic (MD) simulation. The Condensed-Phase Optimized Molecular Potential for Atomistic Simulation Studies (COMPASS) force field was used with the total simulation runs were set 1000 picoseconds run production ensembles. The temperature and pressure set for both ensembles were 298 K and 1 atm respectively. The validity of our model densities data was check and calculated where the deviation must be less than 6%. The comparison between hydrophobic and hydrophilic of the support membrane data was examined by the distance and magnitude of intensity of the Radial Distribution Function (RDF's) trends.
Project description:A practical fabrication technique is presented to tackle the trade-off between the water flux and salt rejection of thin film composite (TFC) reverse osmosis (RO) membranes through controlled creation of a thinner active selective polyamide (PA) layer. The new thin film nano-composite (TFNC) RO membranes were synthesized with multifunctional poly tannic acid-functionalized graphene oxide nanosheets (pTA-f-GO) embedded in its PA thin active layer, which is produced through interfacial polymerization. The incorporation of pTA-f-GOL into the fabricated TFNC membranes resulted in a thinner PA layer with lower roughness and higher hydrophilicity compared to pristine membrane. These properties enhanced both the membrane water flux (improved by 40%) and salt rejection (increased by 8%) of the TFNC membrane. Furthermore, the incorporation of biocidal pTA-f-GO nanosheets into the PA active layer contributed to improving the antibacterial properties by 80%, compared to pristine membrane. The fabrication of the pTA-f-GO nanosheets embedded in the PA layer presented in this study is a very practical, scalable and generic process that can potentially be applied in different types of separation membranes resulting in less energy consumption, increased cost-efficiency and improved performance.
Project description:To improve the filtration performance and properties of organic solvent nanofiltration (OSN) membranes, we firstly introduce nanoporous silica (SiO?) particles into the polyamide (PA) active layer of polysulfone (PSf) membrane via an interfacial polymerization process. Results from the study revealed that introduction of SiO? influenced the properties of PSf/PA-SiO? composite membranes by changing the surface roughness and hydrophilicity. Moreover, results also indicated that nanoporous SiO? modified membranes showed an improved performance of alcohols solvent permeance. The PSf/PA-SiO? composite membrane modified by 0.025 wt % of SiO? 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.
Project description:Nanofiltration (NF) membranes with ultrahigh permeance and high rejection are highly beneficial for efficient desalination and wastewater treatment. Improving water permeance while maintaining the high rejection of state-of-the-art thin film composite (TFC) NF membranes remains a great challenge. Herein, we report the fabrication of a TFC NF membrane with a crumpled polyamide (PA) layer via interfacial polymerization on a single-walled carbon nanotubes/polyether sulfone composite support loaded with nanoparticles as a sacrificial templating material, using metal-organic framework nanoparticles (ZIF-8) as an example. The nanoparticles, which can be removed by water dissolution after interfacial polymerization, facilitate the formation of a rough PA active layer with crumpled nanostructure. The NF membrane obtained thereby exhibits high permeance up to 53.5?l?m-2h-1?bar-1 with a rejection above 95% for Na2SO4, yielding an overall desalination performance superior to state-of-the-art NF membranes reported so far. Our work provides a simple avenue to fabricate advanced PA NF membranes with outstanding performance.
Project description:Improving the performance of desalination membranes requires better measurements of salt permeability in the polyamide separating layer to elucidate the thermodynamic and kinetic components of membrane permselectivity. In this work, electrochemical impedance spectroscopy (EIS) is introduced as a technique to measure the salt permeability and estimate the salt partition coefficient in thin polyamide films created using molecular layer-by-layer deposition. The impedance of supported polyamide films ranging in thickness from 3.5 nm to 28.5 nm were measured in different electrolyte solutions. Impedance spectra were modeled with equivalent circuits containing resistive and capacitive elements associated with the EIS measurement system as well as characteristic low-frequency parallel resistive and capacitive elements that are associated with the polyamide film. The characteristic polyamide membrane resistance increases with film thickness, decreases with solution concentration, and is an order of magnitude greater for a divalent cationic solution than for a monovalent cationic solution. For each polyamide film, salt permeability is calculated from the membrane resistance, and a salt partition coefficient is estimated. At the highest solution concentration measured, which is representative of brackish water desalination conditions, the calculated salt permeabilities range from P s = 1.3 × 10-16 m s-1 to 3.9 × 10-16 m s-1, and the estimated salt partition coefficients range from K s = 0.008 to 0.016. These measurements demonstrate that EIS is a powerful tool for studying membrane permselectivity through the measurement of salt permeability in thin polyamide films.
Project description:The data presented in this paper are produced as part of the original research article entitled "Thin-film composite membrane on a compacted woven backing fabric for pressure assisted osmosis" (Sahebi et al., 2017). This article describes how to fabricate a defect free membrane for forward osmosis (FO) and pressure assisted osmosis (PAO) on the woven mesh backing fabric support. Casting polymer on backing fabric support may limit the interfacial polyemirization due to wrinkled membrane surface. This paper presents data obtained from two different backing fabrics used as support for fabrication of thin film composite FO membrane. Backing fabric support were woven polyester mesh with different opening size. The data include the characterization of the intrinsic properties of the membrane samples, SEM and their performance under FO process. The structural parameters (S value) of the substrate were computed from thickness and porosity of the substrates. Thin film composite (TFC) membrane achieved a water flux of 8.1?L?m2 h-1 in FO process and 37?L?m2 h-1 using 0.5?M NaCl as draw solution (DS) and deionised (DI) water as the feed solution (FS) when applied hydraulic pressure was 10?bar.
Project description:Forward osmosis (FO) is a promising alternative to reverse osmosis (RO) in membrane-based water desalination. In the current study, carboxylated multiwalled carbon nanotubes (MWCNTs) were incorporated in a polyamide (PA) layer formed on top of a polysulfone porous support, resulting in a thin film nanocomposite (TFN) membrane. The amount of MWCNTs was varied (0.01, 0.05, 0.1, and 0.2 wt/vol %). The FO performance was investigated using deionized water as the feed solution and 2 M NaCl as the draw solution. It was found that the carboxylated MWCNTs enhanced the membrane hydrophilicity, surface roughness, and porosity. Such combined effects are believed to have led to enhanced FO water flux. TFN 0.2 showed the highest FO water flux of 73.15 L/m<sup>2</sup> h, an improvement of 67% compared to the blank thin-film composite (TFC) membrane and significantly better than the values reported in the literature. Direct observation by transmission electron microscopy revealed the presence of some open-ended CNTs favorably oriented across the PA layer. Those are believed to have facilitated the transport of water through their inner cores and contributed to the increase in water flux. However, this was at the expense of salt rejection and reverse solute flux performance. The best performing membrane was found to be TFN 0.01. It exhibited a salt rejection of 90.1% with a FO water flux of 50.23 L/m<sup>2</sup> h, which is 13% higher than the TFC membrane, and a reverse solute flux of 2.76 g/m<sup>2</sup> h, which is 21% lower than the TFC membrane. This TFN 0.01 membrane also outperformed the TFN membranes reported in the literature.