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The fabrication of new membrane that is able to produce stable high power density is essential for the development of pressure retarded osmosis (PRO) technology. In this work, thin film composite (TFC) polyetherimide membranes with three different substrate structures were fabricated and characterized. The PRO performance of the resultant membrane was evaluated through two pressure cycle experiments and stability tests. The primary objective of this work is to systematically study PRO membrane’s mechanical stability and mass transfer properties under high operating pressures, which determine the power density of the membrane in the PRO process. Experiments revealed that water permeability ( A p ) and salt permeability ( B p ) under different pressures varied. The A p and B p are better indicators for examining the variation of PRO membrane structure under pressure. Within the operating pressure range of 17.2 bar, the top polyamide layer of TFC PEI-2# membrane mainly experienced a reversible deformation. In the two pressure cycle tests, the water flux, specific salt flux and power density obtained in the upward and downward measurements in each cycle are close to each other. The first cycle and the second cycle also show excellent reproducibility. The membrane was able to maintain almost unchanged water flux and power density of 12.8 W/m 2 at 17.2 bar over the 10 h testing time, suggesting the membrane’s great potential to be used in practical application in the future. [ABSTRACT FROM AUTHOR]

• Ge/graphene heterojunctions were employed to realize flexible NIR detector. • Ultra-thin Ge layer with a polycrystalline structure has been prepared on graphene by using PLD. • Ge/graphene heterojunction was transferred onto a polyimide flexible substrate successfully. • The heterojunction has the enhanced absorption characteristics in the near-infrared band. To fabricate a flexible near-infrared (NIR) photodetector, the Ge/graphene (Ge/Gr) heterojunction was fabricated by using pulsed laser deposition on copper-supported graphene, and then the heterojunction was transferred onto flexible polyimide (PI) substrate. The Ge/Gr heterostructure grown at 530 °C demonstrates a flat surface and good crystalline quality. Compared with the as-grown Ge/Gr heterojunction on Si substrate, the Raman spectra of the transferred Ge/Gr heterojunction have no significant change, which indicates the successful transfer of the heterojunction. The Ge/Gr heterojunction has significantly enhanced absorption characteristics in the VIS-NIR range, exhibits rectification ratio up to 13.5 at ± 3 V and stable photoresponse to the NIR light at zero voltage bias. [ABSTRACT FROM AUTHOR]

Abstract: Hollow fiber membranes with a positively charged nanofiltration (NF)-like selective layer have been successfully fabricated by utilizing asymmetric microporous hollow fibers made of Torlon® polyamide–imide (PAI) material as the porous substrate followed by polyelectrolyte post-treatment using polyethyleneimine (PEI), which has not been reported previously. The reaction between PAI and PEI has been confirmed by experiments. The membrane structure and surface property are carefully tailored by adjusting polymer dope composition, spinning conditions and the post-treatment parameters. These membranes are, subsequently, characterized by a series of standard protocols in terms of membrane morphology, structure, permeability and salt rejection, and are applied in forward osmosis (FO) processes. The newly developed PAI hollow fiber membranes show a pure water permeability of 2.19–2.25L/m2 hbar and reasonable NaCl and MgCl2 rejections of 49% and 94% at 1bar, respectively. It is also found that in FO processes, when using 0.5M MgCl2 as a draw solution and DI water as the feed in the active layer facing feed water (AL-facing-FW) configuration at 23°C, the water fluxes of two PAI FO hollow fiber membranes are 8.36 and 9.74L/m2 h, respectively, and the J S /J V of the two membranes is smaller than 0.4g/L, which is lower than the data of 0.85g/L for commercial FO membrane from Hydration Technologies Inc. (HTI). Different from a neutral membrane, the positively charged FO membrane provides double electric repulsions to the salt transfer through the membrane in the AL-facing-FW configuration, leading to a reduction of salt penetration, while in the active layer facing draw solution (AL-facing-DS) configuration, the positive charges facilitate salt transportation. This study provides a simple and effective approach to make hollow fibers suitable for FO applications. [Copyright &y& Elsevier]

We report that 6FDA-2,6-DAT polyimide can be used to fabricate hollow fiber membranes with excellent performances for CO2/CH4 separation. In order to simplify the hollow fiber fabrication process and verify the feasibility of 6FDA-2,6-DAT hollow fiber membranes for CO2/CH4 separation, a new one-polymer and one-solvent spinning system (6FDA-2,6-DAT/N-methyl-pyrrolidone (NMP)) with much simpler processing conditions has been developed and the separation performance of newly developed 6FDA-2,6-DAT hollow fiber membranes has been further studied under the pure and mixed gas systems.Experimental results reveal that 6FDA-2,6-DAT asymmetric composite hollow fiber membranes have a strong tendency to be plasticized by CO2 and suffer severely physical aging with an initial CO2 permeance of 300 GPU drifting to 76 GPU at the steady state. However, the 6FDA-2,6-DAT asymmetric composite hollow fibers still present impressive ultimate stabilized performance with a CO2/CH4 selectivity of 40 and a CO2 permeance of 59 GPU under mixed gas tests. These results manifest that 6FDA-2,6-DAT polyimide is one of promising membrane material candidates for CO2/CH4 separation application. [Copyright &y& Elsevier]

Abstract: Nanofiltration (NF) membrane process has become increasingly attractive due to their unique characteristics to selectively remove specific compounds or ions. The most commonly NF membranes are negatively charged which is unsuitable for hardness removal. Therefore, the development of novel NF membranes with a positively charged skin has become a key issue for low pressure water softening. In this study, dual layer microporous hollow fiber membranes were fabricated using Torlon poly(amide-imide) (PAI) as the material of the selective outer layer and polyethersulfone (PES) as the material of the porous support inner layer. A positively charged NF-like selective layer was developed by a simple polyelectrolyte cross-linking using polyallylamine (PAAm). The newly developed (PAI–PAAm)–PES dual layer hollow fiber membranes show a salt water permeability of 15.8 L/m2 h bar and high Mg2+ and Ca2+ rejections of 94.2% and 92.3%, respectively, at operating pressure of 2 bar using a 3000 ppm TDS feed solution. This study provides a simple and effective approach to produce positively charged NF hollow fiber membranes for water softening applications with low energy consumption. [Copyright &y& Elsevier]

We have studied the CO2-induced plasticization phenomenon of asymmetric poly(2,6-toluene-2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane diimide) (6FDA-2,6 DAT) hollow fiber membranes for CO2/CH4 applications. Several processing and thermal approaches have been investigated to study their effectiveness to enhance anti-plasticization characteristics. Experimental results indicate that hollow fiber membranes spun at different shear rates and take-up rates cannot effectively suppress the CO2 induced plasticization. Thermally treated 6FDA-2,6 DAT hollow fiber membranes show significant reduction in CO2-induced plasticization. Wide-angle XRD spectra reveal no visible change in d-space after thermal treatment, while solubility data imply no cross-links occurred. Scanning electron microscopy (SEM) pictures illustrate heat treatment results in more compact selective-skin layer and substructure, thus strengthening the anti-plasticization characteristics of hollow fibers. By considering the degree of plasticization, dense-layer thickness, and heat treatment temperature, an optimal temperature of 250 °C (for 5 min) is identified for the heat treatment of 6FDA-2,6 DAT hollow fiber membranes. NMR spectra suggest the cause of forming a highly densified skin after heat treatment is mainly due to chain relaxation and enhanced nodule interaction at elevated temperatures. [Copyright &y& Elsevier]

A scaled-up hollow fibre thin-film composite (TFC) module was successfully developed for organic solvent forward osmosis (OSFO) application in the pharmaceutical industry. The membrane consists of cross-linked P84 polyimide substrate with a polyamide selective layer, formed via interfacial polymerisation. The performance of the lab-scale module was compared to the scaled-up module in reverse osmosis and forward osmosis modes. The results from both tests revealed that the solvent permeability of the scaled-up module decreased while its selectivity increased slightly. This might be caused by the uneven distribution of liquids during interfacial polymerisation, leading to varied membrane performance. The scaled-up module was further tested for OSFO performance using a range of PEG-400 concentrations (0.5–2 M) in acetone and isopropanol as draw solutions. At 2 M PEG-400 concentration, the module demonstrated high isopropanol and acetone permeability of 0.63 LMH and 13.9 LMH, respectively. Moreover, the reverse solute flux of PEG-400 in acetone and isopropanol were relatively low at 0.188 g/l and 0.153 g/l, respectively. The module was further tested for OSFO application in the pharmaceutical industry by concentrating levofloxacin in acetone, using 2 M PEG-400 as draw solution. The process was able to concentrate levofloxacin from 1000 ppm to 16,000 ppm with very low reverse solute flux of 0.178 g/l. Therefore, this work presents a scalable TFC membrane for OSFO application in the pharmaceutical industry. [Display omitted] • Scaled-up module (0.4 m2) of TFC hollow fibre membrane for organic solvent forward osmosis process was successfully fabricated. • High porosity (79%) and low structural parameter (217 μm) for membrane substrate was achieved. • Membrane exhibited excellent acetone and IPA solvent flux of 13.9 LMH and 0.63 LMH, respectively, using a 2 M PEG-400 draw solution. • A pharmaceutical stream was concentrated to a factor of 16 with low specific reverse solute flux [ABSTRACT FROM AUTHOR]

A scaled-up hollow fibre thin-film composite (TFC) module was successfully developed for organic solvent forward osmosis (OSFO) application in the pharmaceutical industry. The membrane consists of cross-linked P84 polyimide substrate with a polyamide selective layer, formed via interfacial polymerisation. The performance of the lab-scale module was compared to the scaled-up module in reverse osmosis and forward osmosis modes. The results from both tests revealed that the solvent permeability of the scaled-up module decreased while its selectivity increased slightly. This might be caused by the uneven distribution of liquids during interfacial polymerisation, leading to varied membrane performance. The scaled-up module was further tested for OSFO performance using a range of PEG-400 concentrations (0.5–2 M) in acetone and isopropanol as draw solutions. At 2 M PEG-400 concentration, the module demonstrated high isopropanol and acetone permeability of 0.63 LMH and 13.9 LMH, respectively. Moreover, the reverse solute flux of PEG-400 in acetone and isopropanol were relatively low at 0.188 g/l and 0.153 g/l, respectively. The module was further tested for OSFO application in the pharmaceutical industry by concentrating levofloxacin in acetone, using 2 M PEG-400 as draw solution. The process was able to concentrate levofloxacin from 1000 ppm to 16,000 ppm with very low reverse solute flux of 0.178 g/l. Therefore, this work presents a scalable TFC membrane for OSFO application in the pharmaceutical industry. [Display omitted] • Scaled-up module (0.4 m2) of TFC hollow fibre membrane for organic solvent forward osmosis process was successfully fabricated. • High porosity (79%) and low structural parameter (217 μm) for membrane substrate was achieved. • Membrane exhibited excellent acetone and IPA solvent flux of 13.9 LMH and 0.63 LMH, respectively, using a 2 M PEG-400 draw solution. • A pharmaceutical stream was concentrated to a factor of 16 with low specific reverse solute flux [ABSTRACT FROM AUTHOR]

Electrospun polymeric membranes are promising substrates for thin-film composite (TFC) membranes due to their unique interconnected pores and high porosity. However, it is still challenging to fabricate desirable electrospun substrates for organic solvent nanofiltration (OSN) owing to the relatively complex processing procedures and the organic operating environment. In this work, solvent-resistant electrospun polyimide (PI) nanofiber substrates were successfully fabricated through electrospinning followed by chemical cross-linking and heat-pressing. The cross-linking step improved the solvent tolerance of the membranes, while the heat-pressing step reduced the substrate pore size and surface roughness. However, it was found that heat-pressing at high temperatures (>140 °C) could degrade the cross-linking of PI, undermining their solvent-resistant property. A polyamide thin film layer was then synthesized on the solvent-resistant electrospun nanofibrous substrates via interfacial polymerization using reactant monomers m -phenylenediamine (MPD) and trimesoyl chloride (TMC). The TFC membranes exhibited excellent acetonitrile and acetone permeabilities of 31.28 ± 1.93 and 26.58 ± 1.13 L m−2 h−1 bar−1, respectively, with acid fuchsin (585 Da) and methyl orange (327 Da) rejections of 98.55 ± 1.24% and 92.42 ± 1.66%, respectively, in acetone. This study successfully demonstrated the potential use of electrospun PI nanofibers substrates for TFC membranes in OSN. [Display omitted] • Solvent resistant nanofibrous PI substrates were prepared by electrospinning followed by chemical cross-linking and heat-pressing. • Heat-pressing influenced the PI substrates' surface properties and solvent resistance, and the optimal point was 140 °C. • Polyamide thin film was synthesized on the PI substrates via interfacial polymerization for OSN application. • Acetone permeability was 26.58 L m−2 h−1 bar−1 with high rejection to acid fuchsin and methyl orange. [ABSTRACT FROM AUTHOR]

Abstract: Polyamide thin film composite (TFC) membranes with tailored porous substrate and rejection layer are promising for forward osmosis (FO) applications. The current study investigates the effect of rejection layer synthesis conditions on the performance of the resulting TFC polyamide FO membranes. The influence of monomer concentrations (i.e., m-phenylenediamine (MPD) and trimesoyl chloride (TMC) concentrations) on the membrane separation properties as well as FO performance was systematically studied. A strong trade-off between the water permeability and salt rejection was observed, where increasing the TMC concentration or reducing the MPD concentration resulted in higher membrane permeability but lower salt rejection. In FO tests, membranes with poor salt rejection had severe solute reverse diffusion, which enhanced the internal concentration polarization (ICP). It was found that the FO water flux was governed by both the membrane water permeability and its solute rejection. For a membrane with higher water permeability but lower solute rejection, the reduced membrane frictional resistance was compensated by the simultaneously more severe solute-reverse-diffusion-induced ICP. The net effect on the FO water flux depends on the competition of these two opposing mechanisms. Under conditions where solute reverse diffusion may cause severe ICP (e.g., high draw solution concentration and high water flux level), membranes need be optimized to achieve a high salt rejection even if this is at the expense of lower water permeability. [Copyright &y& Elsevier]

The separation of CO2/CH4 separation is industrially important especially for natural gas processing. In the past decades, polymeric membranes separation technology has been widely adopted for CO2/CH4 separation. However, polymeric membranes are suffering from plasticization by condensable CO2 molecules. Thus, carbon molecular sieve membranes (CMSMs) with excellent separation performance and stability appear to be a promising candidate for CO2/CH4 separation. A commercially available polyimide, P84 has been chosen as a precursor in preparing carbon membranes for this study. P84 displays a very high selectivity among the polyimides. The carbonization process was carried out at 550–800°C under vacuum environment. WAXD and density measurements were performed to characterize the morphology of carbon membranes. The permeation properties of single and equimolar binary gas mixture through carbon membranes were measured and analyzed. The highest selectivity was attained by carbon membranes pyrolyzed at 800°C, where the pyrolysis temperatures significantly affected the permeation properties of carbon membranes. A comparison of permeation properties among carbon membranes derived from four commercially available polyimides showed that the P84 carbon membranes exhibited the highest separation efficiency for CO2/CH4 separation. The pure gas measurement underestimated the separation efficiency of carbon membranes, due to the restricted diffusion of non-adsorbable gas by adsorbable component in binary mixture. [Copyright &y& Elsevier]

The effects of amidation on gas separation properties of polyimide dense films were investigated. Using 6FDA-durene and 6FDA-durene/mPDA (50:50) as the examples, the amidation was performed by immersing these polyimide dense films in a 10% (w/v) N,N-dimethylaminoethyleneamine (DMEA) hexane solution for a certain period of time at ambient temperature. FTIR spectra indicate the intensities of the characteristic peaks of imide group decrease, while those of amide groups increase with increasing the immersion time. Gas permeabilities of the modified polyimides to He, O2, N2, CO2 and CH4 were measured at 35 °C and the results suggest that the proposed amidation lowers the gas permeabilities of all gases, while improves the gas permselectivities of He/N2 and O2/N2. Experimental results also imply that the effects of amidation on gas permselectivity strongly depend on the polyimide chemical structure. For the gas pairs of CO2/N2 and CO2/CH4, the DMEA modified 6FDA-durene/mPDA (50:50) shows enhanced gas permselectivities, whereas the DMEA modified 6FDA-durene exhibits worse gas permselectivities. Since the amidation by DMEA and the chemical cross-linking modification by p-xylene diamine display similar effects on gas separation properties of modified polyimides, one may conclude that the changes of imide groups to amide groups in the cross-linking process has remarkable effects on gas separation properties. The changes in gas separation properties were discussed in terms of diffusion coefficients and solubility coefficients. [Copyright &y& Elsevier]

We have determined the effects of dope composition, rheology and process conditions on membrane morphology and gas separation performance of asymmetric poly(2,6-toluene-2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane diimide) (6FDA-2,6 DAT) hollow fiber membranes for air and CO2/CH4 applications. Two spinning dope systems were prepared; one is a binary system in N-methyl-2-pyrrolidone (NMP), the other is a ternary system in a mixture of NMP and ethanol (EtOH). Both dopes exhibit non-Newtonian and shear-thinning power-law characteristics. Experimental data show that the shear stress within the spinneret significantly changes the skin and cross-section morphology and separation performance. The degree of changes is more severe in a highly viscous binary system than in an EtOH containing ternary system. For the 6FDA-2,6 DAT/NMP system, both permeances of O2, N2, CO2 and CH4 and selectivities of O2/N2 and CO2/CH4 decrease slightly with an increase in shear rate. While for the 6FDA-2,6 DAT/NMP/EtOH system, similar to the previous case, permeances of all testing gases decrease with increasing shear rate because of shear-induced orientation. However, very interestingly and contradictory to the binary dope system, the CO2/CH4 selectivity increases with increasing shear rate. The difference in selectivity trend is probably due to the fact that the ternary system has EtOH as a non-solvent additive which shortens the precipitation path and reduces the degree of vigorousness during the phase inversion process. Scanning electron microscopy (SEM) pictures show fibers spun from the viscous binary system tend to have more shear-induced defects in high shear rates. In addition, the elongational stress induced by the take up unit has a tendency to induce molecular orientation as well as to create skin surface defects. [Copyright &y& Elsevier]