• Membrane and Water Treatment
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• v.6 no.4
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• pp.309-321
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• 2015

We report in this study the synthesis of mixed matrix reverse osmosis membranes by interfacial polymerization (IP) of thin film nanocomposite (TFNC) on porous polysulfone supports (PS). This paper investigates the synthesis of ZnO nanoparticles (NPs) using the sol-gel processing technique and evaluates the performance of mixed matrix membranes reached by these aerogel NPs. Aqueous m-phenyl diamine (MPD) and organic trimesoyl chloride (TMC)-NPs mixture solutions were used in the IP process. The reaction of MPD and TMC at the interface of PS substrates resulted in the formation of the thin film composite (TFC). NPs of ZnO with a size of about 25 nm were used for the fabrication of the TFNC membranes. These membranes were characterized and evaluated in comparison with neat TFC ones. Their performances were evaluated based on the water permeability and salt rejection. Experimental results indicated that the NPs improved membrane performance under optimal concentration of NPs. By changing the content of the filler, better hydrophilicity was obtained; the contact angle was decreased from $74^{\circ}$ to $32^{\circ}$. Also, the permeate water flux was increased from 26 to 49 L/m2.h when the content of NPs is 0.1 (wt.%) with the maintaining of lower salt passage of 1%.

• Membrane Journal
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• v.31 no.6
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• pp.434-442
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• 2021

Poly(vinylidene fluoride) (PVDF) membrane has a good membrane durability because of its high mechanical resistance, thermal and chemical stability. However, the strong hydrophobic property of PVDF membrane can induce a low water permeability and easy fouling by proteins and organic matters. In order to improve the anti-fouling properties of PVDF membrane, the PVDF mixed matrix asymmetric membranes impregnated with biofunctional material 𝛽-cyclodextrin (𝛽-CD) in the membrane structure were prepared by phase inversion method. The membrane filtration experiments of pure water and BSA solution were performed using the PVDF/𝛽-CD mixed matrix asymmetric membranes prepared according to the 𝛽-CD contents. The experiments showed that the introduction of 𝛽-CD into the PVDF polymer matrix contributed to increase in the hydrophilic property of the PVDF membranes, and this led to the reduction of contact angles and improvement of anti-fouling properties. The PVDF/𝛽-CD membrane which was prepared using the dope solution with a 2 wt% 𝛽-CD content represented 64 L/m²·h of pure water flux, 95% of BSA rejection and maximum 80% of flux enhancements compared to flux results of the pristine PVDF membrane.

• Applied Chemistry for Engineering
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• v.34 no.3
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• pp.213-220
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• 2023

Mixed-matrix membranes (MMMs), which are composed of a polymer matrix filled with high-performance fillers as a dispersed phase, have been intensively studied for gas separations for the past 30 years. It has been demonstrated that MMMs exhibit superior gas separation performance compared to polymer membranes and are more scalable than polycrystalline membranes. Despite their potential, the commercialization of MMMs has yet to be reported due to several challenging issues. One of the major challenges of MMMs is the non-ideal interface between the continuous polymer phase and dispersed phase, which can result in defect formation (i.e., interfacial voids, etc.). With respect, many MMM studies have focused on addressing the issues through scientific approaches. The engineering approaches for facile and effective large-scale fabrication of MMMs, however, have been relatively underestimated. In this review paper, a novel strategy for fabricating MMMs in a facile and scalable manner using in situ metal-organic framework (MOF) formation is introduced. This new MMM fabrication methodology can effectively address the issues facing current MMMs, likely facilitating the commercialization of MMMs.

• Membrane and Water Treatment
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• v.13 no.6
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• pp.259-290
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• 2022

Carbon nanotubes (CNTs), due to their excellent physical, chemical and mechanical properties and their ability to prepare new membranes with attractive properties, have found applications in water and wastewater technology. CNT functionalization, which involves the introduction of different types of functional groups into pure CNTs, improves the capabilities of CNT membranes for water and wastewater treatment. It turns out that CNT-based membranes have many advantages, including enhanced water permeability, high selectivity and anti-fouling properties. However, their full-scale application is still limited by their high cost. With their tremendous separation efficiency, low biofouling potential and ultra-high water flux, CNT membranes have the potential to be a leading technology in water treatment in the future, especially in desalination.

• Membrane and Water Treatment
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• v.10 no.2
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• pp.165-178
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• 2019

Mixed matrix membranes (MMMs) of poly (vinyl alcohol) (PVA) containing certain amounts of H-${\beta}$ zeolite for pervaporation were manufactured by using a solution casting protocol. These zeolite-embedded membranes were then characterized with scanning electron microscope (SEM), X-ray diffraction (XRD) and swelling tests. The membrane separation performance has been examined by means of isopropanol (IPA) dewatering from its highly concentrated aqueous solutions via response surface methodology (RSM). The results have demonstrated that the influences of feed IPA composition (85-95 wt.%), feed temperature ($50-70^{\circ}C$), zeolite loading (15-25 wt.%) and their interactive influences are all statistically significant on both pervaporation flux ($398-1228g/m^2{\cdot}h$) and water/isopropanol separation factor (617-2001). The quadratic models based on the RSM analysis have performed excellently to correlate experimental data with very high determination coefficients and very low relative standard deviations. The optimal pervaporation predictions given by using the RSM models demonstrate a total flux of $953g/m^2{\cdot}h$ and separation factor of 1458, and are excellently verified by experimental results. As reflected by these results, PVA MMMs embedded with hydrophilic $H-{\beta}$ zeolite entities have performed considerably better than its pure counterpart and indicated great potential for isopropanol dehydration applications.

• Membrane Journal
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• v.29 no.1
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• pp.44-50
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• 2019

In this paper, we developed mixed matrix membranes (MMMs) consisting of SBS-g-POEM block-graft copolymer, ionic liquid (EMIMTFSI) and ZIF-8 nanoparticles to separate a $CO_2/N_2$ gas pair. The SBS-g-POEM is a rubbery block-graft copolymer synthesized through low-cost free-radical polymerization. The EMIMTFSI was dissolved into the SBS-g-POEM matrix and solution synthesized ZIF-8 nanoparticles were also dispersed into the copolymer matrix. The physico-chemical properties of manufactured membranes were characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffraction (XRD), which showed that the components were compatible with each other. The gas separation performance was confirmed by time-lag measurements showing $CO_2$ permeability of 537.0 barrer and $CO_2/N_2$ selectivity of 15.2. The result represents the EMIMTFSI and ZIF-8 nanoparticles improves the gas permeability more than two-times, without significantly sacrificing the $CO_2/N_2$ selectivity.

• Macromolecular Research
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• v.15 no.4
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• pp.343-347
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• 2007

Novel composite membranes, which delivered high separation performance for propylene/propane mixtures, were developed by coating inert poly(ethylene-co-propylene) rubber (EPR) onto a porous polyester substrate, followed by the physical distribution of $AgBF_4$. Scanning electron microscopy-wavelength dispersive spectrometer (SEM-WDS) revealed that silver salts were uniformly distributed in the EPR layer. The physical dispersion of the silver salts in the inert polymer matrix, without specific interaction, was characterized by FT-IR and FT-Raman spectroscopy. The high separation performance was presumed to stem from the in-situ dissolution of crystalline silver ionic aggregates into free silver ions, which acted as an active propylene carrier within a propylene environment, leading to facilitated propylene transport through the membranes. The membranes were functional at all silver loading levels, exhibiting an unusually low threshold carrier concentration (less than 0.06 of silver weight fraction). The separation properties of these membranes, i.e. the mixed gas selectivity of propylene/propane ${\sim}55$ and mixed gas permeance ${\sim}7$ GPU, were stable for several days.

• Membrane Journal
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• v.32 no.4
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• pp.218-226
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• 2022

Hydrogen, a carrier of large-capacity chemical and clean energy, is an important industrial gas widely used in the petrochemical industry and fuel cells. In particular, hydrogen is mainly produced from fossil fuels through steam reforming and gasification, and carbon dioxide is generated as a by-product. Therefore, in order to obtain high-purity hydrogen, carbon dioxide should be removed. This review focused on free-standing polymeric membranes and mixed-matrix membranes (MMMs) that separate hydrogen from carbon dioxide reported in units of Barrer [1 Barrer = 10^-10 cm³ (STP) × cm / (cm² × s × cmHg)]. By analyzing various recently reported papers, the structure, morphology, interaction, and preparation method of the membranes are discussed, and the structure-property relationship is understood to help find better membrane materials in the future. Robeson's upper bound limits for hydrogen/carbon dioxide separation were presented through reviewing the performance and characteristics of various separation membranes, and various MMMs that improve separation properties using technologies such as crosslinking, blending and heat treatment were discussed.

• Membrane Journal
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• v.25 no.5
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• pp.373-384
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• 2015

In the past few decades, polymeric membrane has played an important role in gas separation applications. For the separation of $CO_2$, one of greenhouse gases, high permselectivity, long-term stability and scale-up are needed. However, conventional polymeric membranes have shown a trade-off relation between permeability and selectivity while inorganic materials are highly permeable but expensive. Mixed matrix membranes (MMMs) combining the advantages of both polymeric and inorganic materials have become a possible breakthrough for the next-generation gas separation membranes. The MMMs could be either symmetric or asymmetric but the latter is more preferred to improve the permeance. Important factors influencing the MMM fabrication include homogeneous distribution of inorganic particles and good interfacial contact between inorganic filler and organic matrix. Recently, metal organic frameworks (MOFs) have received much attention as a new class of porous crystalline materials and a potential candidate for $CO_2$ separation. Zeolitic imidazolate frameworks (ZIFs), a sub-branch of MOFs, are the most widely used in MMMs due to small particle size and appropriate pore size for $CO_2$ separation. One of the major issues associated with the incorporation of porous particles in a polymeric membrane is to control the microstructure of the porous particle materials such as particle size, orientation, and boundary conditions etc. In this review, major challenges surrounding MMMs and the strategies to tackle these challenges are given in detail.

• Membrane Journal
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• v.30 no.6
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• pp.385-394
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• 2020

In the gas separation process, the separation membranes have to not only show high gas transport and selectivity but also exhibit exceptional stability at high temperature and pressure. However, when the polymeric membranes (particularly, glassy polymers) are exposed to the condensable gases (i.e., CO2, H2S, hydrocarbon, etc.), the polymer chains are prone to swell, leading to low stability. As a result, the plasticization behavior reduces the gas selectivity in the separation of mixture gases at high pressures and thus results in limited applications to the separation processes. To address these issues, many strategies have been studied such as thermal treatment, polymer blending, thermally rearrangement, mixed-matrix membranes, cross-linking, etc. In this review, we will understand the plasticization behavior and suggest potential methods based on the previously reported studies.