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15 pages, 3754 KiB

Open AccessArticle

Preparation of Needleless Electrospinning Polyvinyl Alcohol/Water-Soluble Chitosan Nanofibrous Membranes: Antibacterial Property and Filter Efficiency

by Ching-Wen Lou, Meng-Chen Lin, Chen-Hung Huang, Mei-Feng Lai, Bing-Chiuan Shiu and Jia-Horng Lin

Polymers 2022, 14(5), 1054; https://doi.org/10.3390/polym14051054 - 7 Mar 2022

Cited by 13 | Viewed by 3840

Abstract

Electrospinning is an efficient method of producing nanofibers out of polymers that shows a great potential for the filtration territory. Featuring water-soluble chitosan (WS-CS), a low-pollution process and a self-made needleless machine, PVA/WS-CS nanofibrous membranes were prepared and evaluated for nanofiber diameter, bacteriostatic [...] Read more.

Electrospinning is an efficient method of producing nanofibers out of polymers that shows a great potential for the filtration territory. Featuring water-soluble chitosan (WS-CS), a low-pollution process and a self-made needleless machine, PVA/WS-CS nanofibrous membranes were prepared and evaluated for nanofiber diameter, bacteriostatic property, filtration efficiency, pressure drop, and quality factor. Test results indicate that the minimal fiber diameter was 216.58 ± 58.15 nm. Regardless of the WS-CS concentration, all of the PVA/WS-CS nanofibrous membranes attained a high porosity and a high water vapor transmission rate (WVTR), with a pore size of 12.06–22.48 nm. Moreover, the membranes also exhibit bacteriostatic efficacy against Staphylococcus aureus, an optimal quality factor of 0.0825 Pa⁻¹, and a filtration efficiency as high as 97.0%, that is 72.5% higher than that of common masks. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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17 pages, 2589 KiB

Open AccessArticle

Improving Sustainability of the Griess Reaction by Reagent Stabilization on PDMS Membranes and ZnNPs as Reductor of Nitrates: Application to Different Water Samples

by Lusine Hakobyan, Belén Monforte-Gómez, Yolanda Moliner-Martínez, Carmen Molins-Legua and Pilar Campíns-Falcó

Polymers 2022, 14(3), 464; https://doi.org/10.3390/polym14030464 - 24 Jan 2022

Cited by 7 | Viewed by 4759

Abstract

A new approach based on the use of polydimethylsiloxane (PDMS) membranes doped with Griess reagents for in situ determination of

{NO}_{2}^{-}

and

{NO}_{3}^{-}

^- in real samples is proposed. The influence of some doping compounds, on the properties of [...] Read more.

A new approach based on the use of polydimethylsiloxane (PDMS) membranes doped with Griess reagents for in situ determination of

{NO}_{2}^{-}

and

{NO}_{3}^{-}

^- in real samples is proposed. The influence of some doping compounds, on the properties of the PDMS membranes, such as tetraethyl orthosilicate (TEOS), or/and ionic liquids (OMIM PF₆) has been studied. Membrane characterization was performed. To apply the procedure to

{NO}_{3}^{-}

determination, dispersed Zn nanoparticles (ZnNPs) were employed. The analytical responses were the absorbance or the RGB components from digital images. Good precision (RSD < 8%) and detection limit of 0.01 and 0.5 mgL⁻¹ for

{NO}_{2}^{-}

and

{NO}_{3}^{-}

, respectively, were achieved. The approach was satisfactory when applied to the determination of

{NO}_{2}^{-}

and

{NO}_{3}^{-}

in drinking waters, irrigation and river waters, and waters from canned and fresh vegetables. The results obtained were statistically comparable with those by using nitrate ISE or UV measurement. This approach was transferred satisfactory to 96 wells for multianalysis. This study enables the improvement in the on-site determination of

{NO}_{2}^{-}

and

{NO}_{3}^{-}

in several matrices. It is a sustainable alternative over the reagent derivatizations in solution and presents several advantages such as being versatile, simplicity, low analysis time, cost, and energy efficiency. The response can be detected visually or by portable instruments such as smartphone. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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14 pages, 1745 KiB

Open AccessArticle

Effect of Immobilization of Phenolic Antioxidant on Thermo-Oxidative Stability and Aging of Poly(1-trimethylsilyl-1-propyne) in View of Membrane Application

by Sergey Shishatskiy, Vladimir Makrushin, Ivan Levin, Petra Merten, Samira Matson and Valeriy Khotimskiy

Polymers 2022, 14(3), 462; https://doi.org/10.3390/polym14030462 - 24 Jan 2022

Cited by 8 | Viewed by 2692

Abstract

The effect of phenolic antioxidant Irganox 1076 on the structure and gas permeation behavior of poly(1-trimethylsilyl-1-propyne) (PTMSP) was investigated. Isotropic films as well as thin film composite membranes (TFCM) from pure PTMSP and with added antioxidant (0.02 wt%) were prepared. PTMSP with antioxidant [...] Read more.

The effect of phenolic antioxidant Irganox 1076 on the structure and gas permeation behavior of poly(1-trimethylsilyl-1-propyne) (PTMSP) was investigated. Isotropic films as well as thin film composite membranes (TFCM) from pure PTMSP and with added antioxidant (0.02 wt%) were prepared. PTMSP with antioxidant has a significantly higher thermal degradation stability in comparison to pure polymer. The thermal annealing of isotropic films of PTMSP with antioxidant was carried out at 140 °C. It revealed the stability of gas permeation properties for a minimum of up to 500 h of total heating time after a modest permeation values decrease in the first 48 h. X-ray diffraction data indicate a decrease in interchain distances during the heat treatment of isotropic films and indicate an increase in the packing density of macromolecules during thermally activated relaxation. Isotropic films and TFCMs from pure PTMSP and with antioxidant stabilizer were tested under conditions of constant O₂ and N₂ flow. The physical aging of thick and composite PTMSP membranes point out the necessity of thermal annealing for obtaining PTMSP-based membranes with predictable properties. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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25 pages, 3588 KiB

Open AccessArticle

Investigation of the Side Chain Effect on Gas and Water Vapor Transport Properties of Anthracene-Maleimide Based Polymers of Intrinsic Microporosity

by Esra Caliskan, Sergey Shishatskiy, Silvio Neumann, Volker Abetz and Volkan Filiz

Polymers 2022, 14(1), 119; https://doi.org/10.3390/polym14010119 - 29 Dec 2021

Cited by 8 | Viewed by 2392

Abstract

In the present work, a set of anthracene maleimide monomers with different aliphatic side groups obtained by Diels Alder reactions were used as precursors for a series of polymers of intrinsic microporosity (PIM) based homo- and copolymers that were successfully synthesized and characterized. [...] Read more.

In the present work, a set of anthracene maleimide monomers with different aliphatic side groups obtained by Diels Alder reactions were used as precursors for a series of polymers of intrinsic microporosity (PIM) based homo- and copolymers that were successfully synthesized and characterized. Polymers with different sizes and shapes of aliphatic side groups were characterized by size-exclusion chromatography (SEC), (nuclear magnetic resonance) ¹H-NMR, thermogravimetric (TG) analysis coupled with Fourier-Transform-Infrared (FTIR) spectroscopy (TG-FTIR) and density measurements. The TG-FTIR measurement of the monomer-containing methyl side group revealed that the maleimide group decomposes prior to the anthracene backbone. Thermal treatment of homopolymer methyl-100 thick film was conducted to establish retro-Diels Alder rearrangement of the homopolymer. Gas and water vapor transport properties of homopolymers and copolymers were investigated by time-lag measurements. Homopolymers with bulky side groups (i-propyl-100 and t-butyl-100) experienced a strong impact of these side groups in fractional free volume (FFV) and penetrant permeability, compared to the homopolymers with linear alkyl side chains. The effect of anthracene maleimide derivatives with a variety of aliphatic side groups on water vapor transport is discussed. The maleimide moiety increased the water affinity of the homopolymers. Phenyl-100 exhibited a high water solubility, which is related to a higher amount of aromatic rings in the polymer. Copolymers (methyl-50 and t-butyl-50) showed higher CO₂ and CH₄ permeability compared to PIM-1. In summary, the introduction of bulky substituents increased free volume and permeability whilst the maleimide moiety enhanced the water vapor affinity of the polymers. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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17 pages, 4704 KiB

Open AccessArticle

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

by Cenit Soto, Edwin S. Torres-Cuevas, Alfonso González-Ortega, Laura Palacio, Pedro Prádanos, Benny D. Freeman, Ángel E. Lozano and Antonio Hernandez

Polymers 2021, 13(24), 4343; https://doi.org/10.3390/polym13244343 - 11 Dec 2021

Cited by 6 | Viewed by 2983

Abstract

Mixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (β-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two [...] Read more.

Mixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (β-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two hexafluoropropyilidene moieties, 6FCl-APAF, while the PPN was prepared by reacting triptycene (TRP) and trifluoroacetophenone (TFAP) in a superacid solution. The most probable size of the PPN particles was 75 nm with quite large distributions. The resulting membranes were analyzed by SEM and AFM. Up to 30% PPN loads, both SEM and AFM images confirmed quite planar surfaces, at low scale, with limited roughness. Membranes with high hydrogen permeability and good selectivity for the gas pairs H₂/CH₄ and H₂/N₂ were obtained. For H₂/CO₂, selectivity almost vanished after thermal rearrangement. In all cases, their hydrogen permeability increased with increasing loads of PPN until around 30% PPN with ulterior fairly abrupt decreasing of permeability for all gases studied. Thermal rearrangement of the MMMs resulted in higher permeabilities but lower selectivities. For all the membranes and gas pairs studied, the balance of permeability vs. selectivity surpassed the 1991 Robeson’s upper bound, and approached or even exceeded the 2008 line, for MMMs having 30% PPN loads. In all cases, the HPA-MMMs before thermal rearrangement provided good selectivity versus permeability compromise, similar to their thermally rearranged counterparts but in the zone of high selectivity. For H₂/CH₄, H₂/N₂, these nonthermally rearranged MMMs approach the 2008 Robeson’s upper bound while H₂/CO₂ gives selective transport favoring H₂ on the 1991 Robeson’s bound. Thus, attending to the energy cost of thermal rearrangement, it could be avoided in some cases especially when high selectivity is the target rather than high permeability. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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9 pages, 1925 KiB

Open AccessCommunication

Inner Surface Hydrophilic Modification of PVDF Membrane with Tea Polyphenols/Silica Composite Coating

by Qiang Xu, Xiaoli Ji, Jiaying Tian, Xiaogang Jin and Lili Wu

Polymers 2021, 13(23), 4186; https://doi.org/10.3390/polym13234186 - 30 Nov 2021

Cited by 14 | Viewed by 2712

Abstract

The use of Polyvinylidene fluoride (PVDF) membranes is constrained in wastewater treatment because of their hydrophobic nature. Therefore, a large number of researchers have been working on the hydrophilic modification of their surfaces. In this work, a superhydrophilic tea polyphenols/silica composite coating was [...] Read more.

The use of Polyvinylidene fluoride (PVDF) membranes is constrained in wastewater treatment because of their hydrophobic nature. Therefore, a large number of researchers have been working on the hydrophilic modification of their surfaces. In this work, a superhydrophilic tea polyphenols/silica composite coating was developed by a one-step process. The composite coating can achieve not only superhydrophilic modification of the surface, but also the inner surface of the porous PVDF membrane, which endows the modified membrane with excellent water permeability. The modified membrane possesses ultrahigh water flux (15,353 L·m⁻²·h⁻¹). Besides this, the modified membrane can realize a highly efficient separation of oil/water emulsions (above 96%). Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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11 pages, 4959 KiB

Open AccessArticle

Improvement of Polytetrafluoroethylene Membrane High-Efficiency Particulate Air Filter Performance with Melt-Blown Media

by Euijin Shim, Jeong-Phil Jang, Jai-Joung Moon and Yeonsang Kim

Polymers 2021, 13(23), 4067; https://doi.org/10.3390/polym13234067 - 23 Nov 2021

Cited by 13 | Viewed by 4178

Abstract

Polytetrafluoroethylene (PTFE) membrane filters are widely used in low-load application areas, such as industrial cleanrooms, due to their low initial pressure drop. In this study, melt-blown (MB) nonwoven was introduced as a pre-filtration layer at the front end of a high-efficiency particulate air [...] Read more.

Polytetrafluoroethylene (PTFE) membrane filters are widely used in low-load application areas, such as industrial cleanrooms, due to their low initial pressure drop. In this study, melt-blown (MB) nonwoven was introduced as a pre-filtration layer at the front end of a high-efficiency particulate air (HEPA) filter to improve the filter performance of the PTFE membrane. Pre-filtration reduces the average particle size, which reaches the PTFE membrane and reduces the dust load on the HEPA filters. A comparative analysis of the HEPA filters by composite MB and PTFE was conducted. Regarding the MB composite on the PTFE, low-weight and high-weight MB composites were effective in increasing dust filtration efficiency, and the dust loading capacity of the PTFE composite with high-weight MB increased by approximately three times that of the PTFE membrane. In addition, the filter was installed on an external air conditioner in an actual use environment and showed a high efficiency of 99.984% without a change in differential pressure after 120 days. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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11 pages, 1942 KiB

Open AccessArticle

Investigation on the Microscopic/Macroscopic Mechanical Properties of a Thermally Annealed Nafion^® Membrane

by Tuyet Anh Pham, Seunghoe Koo, Hyunseok Park, Quang Thien Luong, Oh Joong Kwon, Segeun Jang, Sang Moon Kim and Kyeongtae Kim

Polymers 2021, 13(22), 4018; https://doi.org/10.3390/polym13224018 - 20 Nov 2021

Cited by 10 | Viewed by 2906

Abstract

The Nafion^® electrolyte membrane, which provides a proton pathway, is an essential element in fuel cell systems. Thermal treatment without additional additives is widely used to modify the mechanical properties of the membrane, to construct reliable and durable electrolyte membranes in the [...] Read more.

The Nafion^® electrolyte membrane, which provides a proton pathway, is an essential element in fuel cell systems. Thermal treatment without additional additives is widely used to modify the mechanical properties of the membrane, to construct reliable and durable electrolyte membranes in the fuel cell. We measured the microscopic mechanical properties of thermally annealed membranes using atomic force microscopy with the two-point method. Furthermore, the macroscopic property was investigated through tensile tests. The microscopic modulus exceeded the macroscopic modulus over all annealing temperature ranges. Additionally, the measured microscopic modulus increased rapidly near 150 °C and was saturated over that temperature, whereas the macroscopic modulus continuously increased until 250 °C. This mismatched micro/macroscopic reinforcement trend indicates that the internal reinforcement of the clusters is induced first until 150 °C. In contrast, the reinforcement among the clusters, which requires more thermal energy, probably progresses even at a temperature of 250 °C. The results showed that the annealing process is effective for the surface smoothing and leveling of the Nafion^® membrane until 200 °C. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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13 pages, 6658 KiB

Open AccessArticle

Antimicrobial Hydrophilic Membrane Formed by Incorporation of Polymeric Surfactant and Patchouli Oil

by Nasrul Arahman, Cut Meurah Rosnelly, Diki Sukma Windana, Afrillia Fahrina, Silmina Silmina, Teuku Maimun, Sri Mulyati, Umi Fathanah, Sri Aprilia, Muhammad Roil Bilad, Poernomo Gunawan, Wafiq Alni Dzulhijjah and Nur Halimah

Polymers 2021, 13(22), 3872; https://doi.org/10.3390/polym13223872 - 9 Nov 2021

Cited by 11 | Viewed by 2267

Abstract

Membrane properties are highly affected by the composition of the polymer solutions that make up the membrane material and their influence in the filtration performance on the separation or purification process. This paper studies the effects of the addition of pluronic (Plu) and [...] Read more.

Membrane properties are highly affected by the composition of the polymer solutions that make up the membrane material and their influence in the filtration performance on the separation or purification process. This paper studies the effects of the addition of pluronic (Plu) and patchouli oil (PO) in a polyethersulfone (PES) solution on the membrane morphology, membrane hydrophilicity, and filtration performance in the pesticide removal compound in the water sample. Three types of membranes with the composition of PES, PES + Plu, and PES + Plu + patchouli oil were prepared through a polymer phase inversion technique in an aqueous solvent. The resulting membranes were then analyzed and tested for their mechanical properties, hydrophilicity, antimicrobial properties, and filtration performance (cross-flow ultrafiltration). The results show that all of the prepared membranes could reject 75% of the pesticide. The modification of the PES membrane with Plu was shown to increase the overall pore size by altering the pore morphology of the pristine PES, which eventually increased the permeation flux of the ultrafiltration process. Furthermore, patchouli oil added antimicrobial properties, potentially minimizing the biofilm formation on the membrane surface. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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14 pages, 2555 KiB

Open AccessArticle

Continuous Blown Film Preparation of High Starch Content Composite Films with High Ultraviolet Aging Resistance and Excellent Mechanical Properties

by Bowen Lin, Chengqiang Li, Fangping Chen and Changsheng Liu

Polymers 2021, 13(21), 3813; https://doi.org/10.3390/polym13213813 - 4 Nov 2021

Cited by 11 | Viewed by 2788

Abstract

Starch/PBAT blown films with high ultraviolet aging resistance and excellent mechanical properties were prepared by introducing lignin with polyurethane prepolymer (PUP) as a starch modifier and physical compatibilizer and 4,4′–methylene diphenyl diisocyanate (MDI) as a crosslinker. Starch was modified by reacting the NCO [...] Read more.

Starch/PBAT blown films with high ultraviolet aging resistance and excellent mechanical properties were prepared by introducing lignin with polyurethane prepolymer (PUP) as a starch modifier and physical compatibilizer and 4,4′–methylene diphenyl diisocyanate (MDI) as a crosslinker. Starch was modified by reacting the NCO groups of the PUP with the OH groups of the starch to form a carbamate bond. The mechanical properties, hydrophobic properties, ultraviolet barrier, ultraviolet aging properties and microscopic morphology of starch/PBAT films with different contents of lignin were investigated. The results showed that the starch/PBAT films were blown continuously. The addition of lignin did not decrease the mechanical properties. On the contrary, the film with 1% lignin possessed the excellent mechanical properties with longitudinal tensile strength of 15.87 MPa and the elongation at a break of 602.21%. In addition, the higher the lignin content, the better the UV blocking effect. The introduction of lignin did not affect the crystalline properties but improved the hydrophilic properties and sealing strength of the high starch content composite films. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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19 pages, 4395 KiB

Open AccessArticle

H⁺-Conducting Aromatic Multiblock Copolymer and Blend Membranes and Their Application in PEM Electrolysis

by Johannes Bender, Britta Mayerhöfer, Patrick Trinke, Boris Bensmann, Richard Hanke-Rauschenbach, Katica Krajinovic, Simon Thiele and Jochen Kerres

Polymers 2021, 13(20), 3467; https://doi.org/10.3390/polym13203467 - 9 Oct 2021

Cited by 3 | Viewed by 2856

Abstract

As an alternative to common perfluorosulfonic acid-based polyelectrolytes, we present the synthesis and characterization of proton exchange membranes based on two different concepts: (i) Covalently bound multiblock-co-ionomers with a nanophase-separated structure exhibit tunable properties depending on hydrophilic and hydrophobic components’ ratios. Here, the [...] Read more.

As an alternative to common perfluorosulfonic acid-based polyelectrolytes, we present the synthesis and characterization of proton exchange membranes based on two different concepts: (i) Covalently bound multiblock-co-ionomers with a nanophase-separated structure exhibit tunable properties depending on hydrophilic and hydrophobic components’ ratios. Here, the blocks were synthesized individually via step-growth polycondensation from either partially fluorinated or sulfonated aromatic monomers. (ii) Ionically crosslinked blend membranes of partially fluorinated polybenzimidazole and pyridine side-chain-modified polysulfones combine the hydrophilic component’s high proton conductivities with high mechanical stability established by the hydrophobic components. In addition to the polymer synthesis, membrane preparation, and thorough characterization of the obtained materials, hydrogen permeability is determined using linear sweep voltammetry. Furthermore, initial in situ tests in a PEM electrolysis cell show promising cell performance, which can be increased by optimizing electrodes with regard to binders for the respective membrane material. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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15 pages, 5013 KiB

Open AccessArticle

Novel Cellulose Triacetate (CTA)/Cellulose Diacetate (CDA) Blend Membranes Enhanced by Amine Functionalized ZIF-8 for CO₂ Separation

by Ayesha Raza, Susilo Japip, Can Zeng Liang, Sarah Farrukh, Arshad Hussain and Tai-Shung Chung

Polymers 2021, 13(17), 2946; https://doi.org/10.3390/polym13172946 - 31 Aug 2021

Cited by 16 | Viewed by 3908

Abstract

Currently, cellulose acetate (CA) membranes dominate membrane-based CO₂ separation for natural gas purification due to their economical and green nature. However, their lower CO₂ permeability and ease of plasticization are the drawbacks. To overcome these weaknesses, we have developed high-performance mixed [...] Read more.

Currently, cellulose acetate (CA) membranes dominate membrane-based CO₂ separation for natural gas purification due to their economical and green nature. However, their lower CO₂ permeability and ease of plasticization are the drawbacks. To overcome these weaknesses, we have developed high-performance mixed matrix membranes (MMMs) consisting of cellulose triacetate (CTA), cellulose diacetate (CDA), and amine functionalized zeolitic imidazolate frameworks (NH₂-ZIF-8) for CO₂ separation. The NH₂-ZIF-8 was chosen as a filler because (1) its pore size is between the kinetic diameters of CO₂ and CH₄ and (2) the NH₂ groups attached on the surface of NH₂-ZIF-8 have good affinity with CO₂ molecules. The incorporation of NH₂-ZIF-8 in the CTA/CDA blend matrix improved both the gas separation performance and plasticization resistance. The optimized membrane containing 15 wt.% of NH₂-ZIF-8 had a CO₂ permeability of 11.33 Barrer at 35 °C under the trans-membrane pressure of 5 bar. This is 2-fold higher than the pristine membrane, while showing a superior CO₂/CH₄ selectivity of 33. In addition, the former had 106% higher CO₂ plasticization resistance of up to about 21 bar and an impressive mixed gas CO₂/CH₄ selectivity of about 40. Therefore, the newly fabricated MMMs based on the CTA/CDA blend may have great potential for CO₂ separation in the natural gas industry. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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15 pages, 24852 KiB

Open AccessArticle

Polyphenylsulfone (PPSU)-Based Copolymeric Membranes: Effects of Chemical Structure and Content on Gas Permeation and Separation

by Fan Feng, Can-Zeng Liang, Ji Wu, Martin Weber, Christian Maletzko, Sui Zhang and Tai-Shung Chung

Polymers 2021, 13(16), 2745; https://doi.org/10.3390/polym13162745 - 16 Aug 2021

Cited by 20 | Viewed by 4398

Abstract

Although various polymer membrane materials have been applied to gas separation, there is a trade-off relationship between permeability and selectivity, limiting their wider applications. In this paper, the relationship between the gas permeation behavior of polyphenylsulfone(PPSU)-based materials and their chemical structure for gas [...] Read more.

Although various polymer membrane materials have been applied to gas separation, there is a trade-off relationship between permeability and selectivity, limiting their wider applications. In this paper, the relationship between the gas permeation behavior of polyphenylsulfone(PPSU)-based materials and their chemical structure for gas separation has been systematically investigated. A PPSU homopolymer and three kinds of 3,3′,5,5′-tetramethyl-4,4′-biphenol (TMBP)-based polyphenylsulfone (TMPPSf) copolymers were synthesized by controlling the TMBP content. As the TMPPSf content increases, the inter-molecular chain distance (or d-spacing value) increases. Data from positron annihilation life-time spectroscopy (PALS) indicate the copolymer with a higher TMPPSf content has a larger fractional free volume (FFV). The logarithm of their O₂, N₂, CO₂, and CH₄ permeability was found to increase linearly with an increase in TMPPSf content but decrease linearly with increasing 1/FFV. The enhanced permeability results from the increases in both sorption coefficient and gas diffusivity of copolymers. Interestingly, the gas permeability increases while the selectivity stays stable due to the presence of methyl groups in TMPPSf, which not only increases the free volume but also rigidifies the polymer chains. This study may provide a new strategy to break the trade-off law and increase the permeability of polymer materials largely. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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13 pages, 3511 KiB

Open AccessArticle

Excellent Performances of Composite Polymer Electrolytes with Porous Vinyl-Functionalized SiO₂ Nanoparticles for Lithium Metal Batteries

by Hui Zhan, Mengjun Wu, Rui Wang, Shuohao Wu, Hao Li, Tian Tian and Haolin Tang

Polymers 2021, 13(15), 2468; https://doi.org/10.3390/polym13152468 - 27 Jul 2021

Cited by 17 | Viewed by 3634

Abstract

Composite polymer electrolytes (CPEs) incorporate the advantages of solid polymer electrolytes (SPEs) and inorganic solid electrolytes (ISEs), which have shown huge potential in the application of safe lithium-metal batteries (LMBs). Effectively avoiding the agglomeration of inorganic fillers in the polymer matrix during the [...] Read more.

Composite polymer electrolytes (CPEs) incorporate the advantages of solid polymer electrolytes (SPEs) and inorganic solid electrolytes (ISEs), which have shown huge potential in the application of safe lithium-metal batteries (LMBs). Effectively avoiding the agglomeration of inorganic fillers in the polymer matrix during the organic–inorganic mixing process is very important for the properties of the composite electrolyte. Herein, a partial cross-linked PEO-based CPE was prepared by porous vinyl-functionalized silicon (p-V-SiO₂) nanoparticles as fillers and poly (ethylene glycol diacrylate) (PEGDA) as cross-linkers. By combining the mechanical rigidity of ceramic fillers and the flexibility of PEO, the as-made electrolyte membranes had excellent mechanical properties. The big special surface area and pore volume of nanoparticles inhibited PEO recrystallization and promoted the dissolution of lithium salt. Chemical bonding improved the interfacial compatibility between organic and inorganic materials and facilitated the homogenization of lithium-ion flow. As a result, the symmetric Li|CPE|Li cells could operate stably over 450 h without a short circuit. All solid Li|LiFePO₄ batteries were constructed with this composite electrolyte and showed excellent rate and cycling performances. The first discharge-specific capacity of the assembled battery was 155.1 mA h g⁻¹, and the capacity retention was 91% after operating for 300 cycles at 0.5 C. These results demonstrated that the chemical grafting of porous inorganic materials and cross-linking polymerization can greatly improve the properties of CPEs. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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19 pages, 5419 KiB

Open AccessArticle

Novel Poly(ionic liquid) Augmented Membranes for Unconventional Aqueous Phase Applications in Fractionation of Dyes and Sugar

by Sandrina DePaz, Arijit Sengupta, Yu-Hsuan Chiao and Sumith Ranil Wickramasinghe

Polymers 2021, 13(14), 2366; https://doi.org/10.3390/polym13142366 - 19 Jul 2021

Cited by 10 | Viewed by 2672

Abstract

Poly(ionic) liquid (PIL) augmented membranes were fabricated through self-polymerization of 2-vinyl pyridine and 4-vinyl pyridine followed by dopamine triggered polymerization and bridging with inert polyamide support. The resulting membranes acquired a positive surface charge with a high degree of hydrophilicity. Fourier transformed Infra-red [...] Read more.

Poly(ionic) liquid (PIL) augmented membranes were fabricated through self-polymerization of 2-vinyl pyridine and 4-vinyl pyridine followed by dopamine triggered polymerization and bridging with inert polyamide support. The resulting membranes acquired a positive surface charge with a high degree of hydrophilicity. Fourier transformed Infra-red (FTIR) and Energy dispersive X-ray (EDX) spectroscopic investigation revealed the successful augmentation of PIL surface layer, whereas surface morphology was investigated through scanning electron microscopy (SEM) imaging. This manuscript demonstrates pi electron-induced separation of dyes with the trend in permeability: Coomassie Brilliant Blue G (CBBHG) > Remazol Brilliant Blue R (RBBR) > Eichrome Black T (EBT) > Congo Red (CR). CBBG exhibited extended conjugation over large aromatic domain. RBBR and EBT were associated withtheelectron-donating -NH₂ group and electron-withdrawing -NO₂ group, respectively, hence pi electron density on aromatic ring varied. The steric repulsion between two pairs of ortho hydrogens (Hs) in biphenyl moieties of CR resulted in deviation of planarity and hence aromaticity leading to the lowest permeability. The sugar fractionation followed the trend: Galactose > Mannose > Fructose > Glucose > Xylose. More hydroxyl (-OH) groups in sugars and their conformational alignment in the same direction, exhibited more lone pair of electrons leading to more interaction with PIL and hence better permeability. Pentose showed poorer permeation than hexose, whereas aldose showed better permeation than ketose. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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13 pages, 1713 KiB

Open AccessArticle

Patterned Membranes for Proton Exchange Membrane Fuel Cells Working at Low Humidity

by Oliver Fernihough, Holly Cheshire, Jean-Michel Romano, Ahmed Ibrahim, Ahmad El-Kharouf and Shangfeng Du

Polymers 2021, 13(12), 1976; https://doi.org/10.3390/polym13121976 - 16 Jun 2021

Cited by 3 | Viewed by 2449

Abstract

High performing proton exchange membrane fuel cells (PEMFCs) that can operate at low relative humidity is a continuing technical challenge for PEMFC developers. In this work, micro-patterned membranes are demonstrated at the cathode side by solution casting techniques using stainless steel moulds with [...] Read more.

High performing proton exchange membrane fuel cells (PEMFCs) that can operate at low relative humidity is a continuing technical challenge for PEMFC developers. In this work, micro-patterned membranes are demonstrated at the cathode side by solution casting techniques using stainless steel moulds with laser-imposed periodic surface structures (LIPSS). Three types of patterns, lotus, lines, and sharklet, are investigated for their influence on the PEMFC power performance at varying humidity conditions. The experimental results show that the cathode electrolyte pattern, in all cases, enhances the fuel cell power performance at 100% relative humidity (RH). However, only the sharklet pattern exhibits a significant improvement at 25% RH, where a peak power density of 450 mW cm⁻² is recorded compared with 150 mW cm⁻² of the conventional flat membrane. The improvements are explored based on high-frequency resistance, electrochemically active surface area (ECSA), and hydrogen crossover by in situ membrane electrode assembly (MEA) testing. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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17 pages, 25180 KiB

Open AccessArticle

Study of Polyvinyl Alcohol-SiO₂ Nanoparticles Polymeric Membrane in Wastewater Treatment Containing Zinc Ions

by Simona Căprărescu, Cristina Modrogan, Violeta Purcar, Annette Madelene Dăncilă and Oanamari Daniela Orbuleț

Polymers 2021, 13(11), 1875; https://doi.org/10.3390/polym13111875 - 4 Jun 2021

Cited by 29 | Viewed by 3812

Abstract

The main goal of the present paper was to synthesize the polyvinyl alcohol-SiO₂ nanoparticles polymeric membrane by wet-phase inversion method. The efficiency of prepared membranes (without and with SiO₂) was investigated using a versatile laboratory electrodialysis system filled with simulated [...] Read more.

The main goal of the present paper was to synthesize the polyvinyl alcohol-SiO₂ nanoparticles polymeric membrane by wet-phase inversion method. The efficiency of prepared membranes (without and with SiO₂) was investigated using a versatile laboratory electrodialysis system filled with simulated wastewaters that contain zinc ions. All experiments were performed at following conditions: the applied voltage at electrodes of 5, 10 and 15 V, a concentration of zinc ions solution of 2 g L⁻¹, time for each test of 1 h and at room temperature. The demineralization rate, extraction percentage of zinc ions, current efficiency and energy consumption were determined. The polymeric membranes were characterized by Fourier Transforms Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR), Scanning Electron Microscopy (SEM) and Electrochemical Impedance Spectroscopy (EIS). The higher value of percentage removal of zinc ions (over 65%) was obtained for the polymeric membrane with SiO₂ nanoparticles, at 15 V. The FTIR-ATR spectra show a characteristic peak located at ~1078 cm⁻¹ assigned to the Si-O-Si asymmetrical stretching. SEM images of the polymeric membrane with SiO₂ nanoparticles show that the nanoparticles and polymer matrix were well compatible. The impedance results indicated that the SiO₂ nanoparticles induced the higher proton conductivity. The final polymeric membranes can be used for the removal of various metallic ions, dyes, organic or inorganic colloids, bacteria or other microorganisms from different natural waters and wastewaters. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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12 pages, 20935 KiB

Open AccessArticle

Cosolvent-Driven Interfacial Polymerization for Superior Separation Performance of Polyurea-Based Pervaporation Membrane

by Manuel Reyes De Guzman, Micah Belle Marie Yap Ang, Shu-Hsien Huang, Fang-Chi Hu, Yu-Hsuan Chiao, Hui-An Tsai and Kueir-Rarn Lee

Polymers 2021, 13(8), 1179; https://doi.org/10.3390/polym13081179 - 7 Apr 2021

Cited by 7 | Viewed by 2885

Abstract

A thin-film composite (TFC) polyurea membrane was fabricated for the dehydration of an aqueous tetrahydrofuran (THF) solution through interfacial polymerization, wherein polyethyleneimine (a water-soluble amine monomer) and m-xylene diisocyanate (an oil-soluble diisocyanate monomer) were reacted on the surface of a modified polyacrylonitrile (mPAN) [...] Read more.

A thin-film composite (TFC) polyurea membrane was fabricated for the dehydration of an aqueous tetrahydrofuran (THF) solution through interfacial polymerization, wherein polyethyleneimine (a water-soluble amine monomer) and m-xylene diisocyanate (an oil-soluble diisocyanate monomer) were reacted on the surface of a modified polyacrylonitrile (mPAN) substrate. Cosolvents were used to tailor the membrane properties and increase the membrane permeation flux. Four types of alcohols that differed in the number of carbon (methanol, ethanol, isopropanol, and tert-butanol) were added as cosolvents, serving as swelling agents, to the aqueous-phase monomer solution, and their effect on the membrane properties and pervaporation separation was discussed. Attenuated total reflection Fourier transform infrared spectroscopy confirmed the formation of a polyurea layer on mPAN. Field emission scanning electron microscopy and surface water contact angle analysis indicated no change in the membrane morphology and hydrophilicity, respectively, despite the addition of cosolvents for interfacial polymerization. The TFC membrane produced when ethanol was the cosolvent exhibited the highest separation performance (permeation flux = 1006 ± 103 g·m⁻²·h⁻¹; water concentration in permeate = 98.8 ± 0.3 wt.%) for an aqueous feed solution containing 90 wt.% THF at 25 °C. During the membrane formation, ethanol caused the polyurea layer to loosen and to acquire a certain degree of cross-linking. The optimal fabrication conditions were as follows: 10 wt.% ethanol as cosolvent; membrane curing temperature = 50 °C; membrane curing time = 30 min. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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20 pages, 5296 KiB

Open AccessArticle

Molecular Mobility in Oriented and Unoriented Membranes Based on Poly[2-(Aziridin-1-yl)ethanol]

by Roberto Teruel-Juanes, Krzysztof Artur Bogdanowicz, Jose D. Badia, Victor Sáenz de Juano-Arbona, Robert Graf, Jose A. Reina, Marta Giamberini and Amparo Ribes-Greus

Polymers 2021, 13(7), 1060; https://doi.org/10.3390/polym13071060 - 28 Mar 2021

Cited by 5 | Viewed by 2066

Abstract

Unoriented and oriented membranes based on dendronized polymers and copolymers obtained by chemical modification of poly[2-(aziridin-1-yl) ethanol] (PAZE) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate were considered. DSC, XRD, CP-MAS NMR and DETA, contribute to characterize the tendency to crystallize, the molecular mobility of [...] Read more.

Unoriented and oriented membranes based on dendronized polymers and copolymers obtained by chemical modification of poly[2-(aziridin-1-yl) ethanol] (PAZE) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate were considered. DSC, XRD, CP-MAS NMR and DETA, contribute to characterize the tendency to crystallize, the molecular mobility of the benzyloxy substituent, the dendritic liquid crystalline group and the clearing transition. The orientation of the mesogenic chain somewhat hindered this molecular motion, especially in the full substituted PAZE. The fragility, free volume and thermal expansion coefficients of these membranes near the glass transition are related to the orientation and the addition of the dendritic groups. PAZE-based membranes combine both order and mobility on a supramolecular and macroscopic level, controlled by the dendritic group and the thermal orientation, and open the possibility of preparing membranes with proper channel mobility that promotes selective ionic transport. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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13 pages, 5920 KiB

Open AccessArticle

Optimal Performance of Thin-Film Composite Nanofiltration-Like Forward Osmosis Membranes Set Off by Changing the Chemical Structure of Diamine Reacted with Trimesoyl Chloride through Interfacial Polymerization

by Manuel Reyes De Guzman, Micah Belle Marie Yap Ang, Shu-Hsien Huang, Qing-Yi Huang, Yu-Hsuan Chiao and Kueir-Rarn Lee

Polymers 2021, 13(4), 544; https://doi.org/10.3390/polym13040544 - 12 Feb 2021

Cited by 6 | Viewed by 3445

Abstract

Thin-film composite (TFC) polyamide membranes formed through interfacial polymerization can function more efficiently by tuning the chemical structure of participating monomers. Accordingly, three kinds of diamine monomers were considered to take part in interfacial polymerization. Each diamine was reacted with trimesoyl chloride (TMC) [...] Read more.

Thin-film composite (TFC) polyamide membranes formed through interfacial polymerization can function more efficiently by tuning the chemical structure of participating monomers. Accordingly, three kinds of diamine monomers were considered to take part in interfacial polymerization. Each diamine was reacted with trimesoyl chloride (TMC) to manufacture TFC polyamide nanofiltration (NF)-like forward osmosis (FO) membranes. The diamines differed in chemical structure; the functional group present between the terminal amines was classified as follows: aliphatic group of 1,3-diaminopropane (DAPE); cyclohexane in 1,3-cyclohexanediamine (CHDA); and aromatic or benzene ring in m-phenylenediamine (MPD). For FO tests, deionized water and 1 M aqueous sodium sulfate solution were used as feed and draw solution, respectively. Interfacial polymerization conditions were also varied: concentrations of water and oil phases, time of contact between the water-phase solution and the membrane substrate, and polymerization reaction time. The resultant membranes were characterized using attenuated total reflectance-Fourier transform infrared spectroscopy, field emission scanning electron microscopy, atomic force microscopy, and surface contact angle measurement to identify the chemical structure, morphology, roughness, and hydrophilicity of the polyamide layer, respectively. The results of FO experiments revealed that among the three diamine monomers, CHDA turned out to be the most effective, as it led to the production of TFC NF-like FO membrane with optimal performance. Then, the following optimum conditions were established for the CHDA-based membrane: contact between 2.5 wt.% aqueous CHDA solution and polysulfone (PSf) substrate for 2 min, and polymerization reaction between 1 wt.% TMC solution and 2.5 wt.% CHDA solution for 30 s. The composite CHDA-TMC/PSf membrane delivered a water flux (Jw) of 18.24 ± 1.33 LMH and a reverse salt flux (Js) of 5.75 ± 1.12 gMH; therefore, Js/Jw was evaluated to be 0.32 ± 0.07 (g/L). Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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15 pages, 5394 KiB

Open AccessArticle

Development of Inorganic Particle-Filled Polypropylene/High Density Polyethylene Membranes via Multilayer Co-Extrusion and Stretching

by Pilar Castejón, Marcelo Antunes and David Arencón

Polymers 2021, 13(2), 306; https://doi.org/10.3390/polym13020306 - 19 Jan 2021

Cited by 6 | Viewed by 3514

Abstract

This work is made to ascertain the effects of mineral fillers, namely calcium carbonate and talc, on the morphology and properties of multilayer polypropylene (PP)/high-density polyethylene (HDPE) porous membranes. Multilayer membranes were prepared using the three-stage Melt-Extrusion, Annealing and Uniaxial Stretching (MEAUS) process. [...] Read more.

This work is made to ascertain the effects of mineral fillers, namely calcium carbonate and talc, on the morphology and properties of multilayer polypropylene (PP)/high-density polyethylene (HDPE) porous membranes. Multilayer membranes were prepared using the three-stage Melt-Extrusion, Annealing and Uniaxial Stretching (MEAUS) process. The orientation of PP’s crystalline phase was affected by both the flow-induced crystallization and the heterogeneous nucleation promoted by the fillers. A synergistic effect was observed in the filled samples due to the generation of pores after the stretching-induced lamellae separation and the debonding of mineral fillers from the polymeric matrix. The fillers increased the porous surface, leading to an increase of permeance to air, being this effect more marked at higher filler contents. Talc showed a higher efficiency to create porous surfaces when compared to calcium carbonate. The thermal stability of the membranes increased with filler addition, as well as their stiffness and strength. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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46 pages, 4344 KiB

Open AccessReview

Fouling Prevention in Polymeric Membranes by Radiation Induced Graft Copolymerization

by Muhammad Nidzhom Zainol Abidin, Mohamed Mahmoud Nasef and Takeshi Matsuura

Polymers 2022, 14(1), 197; https://doi.org/10.3390/polym14010197 - 4 Jan 2022

Cited by 14 | Viewed by 3763

Abstract

The application of membrane processes in various fields has now undergone accelerated developments, despite the presence of some hurdles impacting the process efficiency. Fouling is arguably the main hindrance for a wider implementation of polymeric membranes, particularly in pressure-driven membrane processes, causing higher [...] Read more.

The application of membrane processes in various fields has now undergone accelerated developments, despite the presence of some hurdles impacting the process efficiency. Fouling is arguably the main hindrance for a wider implementation of polymeric membranes, particularly in pressure-driven membrane processes, causing higher costs of energy, operation, and maintenance. Radiation induced graft copolymerization (RIGC) is a powerful versatile technique for covalently imparting selected chemical functionalities to membranes’ surfaces, providing a potential solution to fouling problems. This article aims to systematically review the progress in modifications of polymeric membranes by RIGC of polar monomers onto membranes using various low- and high-energy radiation sources (UV, plasma, γ-rays, and electron beam) for fouling prevention. The feasibility of the modification method with respect to physico-chemical and antifouling properties of the membrane is discussed. Furthermore, the major challenges to the modified membranes in terms of sustainability are outlined and the future research directions are also highlighted. It is expected that this review would attract the attention of membrane developers, users, researchers, and scientists to appreciate the merits of using RIGC for modifying polymeric membranes to mitigate the fouling issue, increase membrane lifespan, and enhance the membrane system efficiency. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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28 pages, 3178 KiB

Open AccessReview

Recent Progress in the Membrane Distillation and Impact of Track-Etched Membranes

by Arman B. Yeszhanov, Ilya V. Korolkov, Saule S. Dosmagambetova, Maxim V. Zdorovets and Olgun Güven

Polymers 2021, 13(15), 2520; https://doi.org/10.3390/polym13152520 - 30 Jul 2021

Cited by 27 | Viewed by 3741

Abstract

Membrane distillation (MD) is a rapidly developing field of research and finds applications in desalination of water, purification from nonvolatile substances, and concentration of various solutions. This review presents data from recent studies on the MD process, MD configuration, the type of membranes [...] Read more.

Membrane distillation (MD) is a rapidly developing field of research and finds applications in desalination of water, purification from nonvolatile substances, and concentration of various solutions. This review presents data from recent studies on the MD process, MD configuration, the type of membranes and membrane hydrophobization. Particular importance has been placed on the methods of hydrophobization and the use of track-etched membranes (TeMs) in the MD process. Hydrophobic TeMs based on poly(ethylene terephthalate) (PET), poly(vinylidene fluoride) (PVDF) and polycarbonate (PC) have been applied in the purification of water from salts and pesticides, as well as in the concentration of low-level liquid radioactive waste (LLLRW). Such membranes are characterized by a narrow pore size distribution, precise values of the number of pores per unit area and narrow thickness. These properties of membranes allow them to be used for more accurate water purification and as model membranes used to test theoretical models (for instance LEP prediction). Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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18 pages, 2564 KiB

Open AccessReview

Application of Zwitterions in Forward Osmosis: A Short Review

by Yu-Hsuan Chiao, Arijit Sengupta, Micah Belle Marie Yap Ang, Shu-Ting Chen, Teow Yeit Haan, Jorge Almodovar, Wei-Song Hung and S. Ranil Wickramasinghe

Polymers 2021, 13(4), 583; https://doi.org/10.3390/polym13040583 - 15 Feb 2021

Cited by 13 | Viewed by 4262

Abstract

Forward osmosis (FO) is an important desalination method to produce potable water. It was also used to treat different wastewater streams, including industrial as well as municipal wastewater. Though FO is environmentally benign, energy intensive, and highly efficient; it still suffers from four [...] Read more.

Forward osmosis (FO) is an important desalination method to produce potable water. It was also used to treat different wastewater streams, including industrial as well as municipal wastewater. Though FO is environmentally benign, energy intensive, and highly efficient; it still suffers from four types of fouling namely: organic fouling, inorganic scaling, biofouling and colloidal fouling or a combination of these types of fouling. Membrane fouling may require simple shear force and physical cleaning for sufficient recovery of membrane performance. Severe fouling may need chemical cleaning, especially when a slimy biofilm or severe microbial colony is formed. Modification of FO membrane through introducing zwitterionic moieties on the membrane surface has been proven to enhance antifouling property. In addition, it could also significantly improve the separation efficiency and longevity of the membrane. Zwitterion moieties can also incorporate in draw solution as electrolytes in FO process. It could be in a form of a monomer or a polymer. Hence, this review comprehensively discussed several methods of inclusion of zwitterionic moieties in FO membrane. These methods include atom transfer radical polymerization (ATRP); second interfacial polymerization (SIP); coating and in situ formation. Furthermore, an attempt was made to understand the mechanism of improvement in FO performance by zwitterionic moieties. Finally, the future prospective of the application of zwitterions in FO has been discussed. Full article

(This article belongs to the Special Issue Advanced Polymer Membranes)

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