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Development, Investigation and Application of Novel Polymer Membranes

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A special issue of Membranes (ISSN 2077-0375). This special issue belongs to the section "Polymeric Membranes".

Deadline for manuscript submissions: closed (31 July 2022) | Viewed by 28266

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Dr. Anastasia Penkova

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Department of Analytical Chemistry, Institute of Chemistry, St. Petersburg State University, 7/9 Universitetskaya nab., 199034 St. Petersburg, Russia
Interests: polymer membranes; nanocomposites; pervaporation; ultrafiltration; gas separation; nanofiltration; thermodynamics and kinetics of nonequilibrium processes; layer by layer; bulk modification; surface modification; mixed matrix membranes; plasma treatment; dehydration; water treatment
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Dr. Tatiana Plisko

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Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, Belarus
Interests: polymer membrane; polymer membrane modification; membrane separation processes; ultrafiltration; pervaporation; nanofiltration; gas separation; thin film composite membranes; biodegradable polymers; smart membranes; smart polymers; mixed matrix membranes; polymer solutions
Special Issues, Collections and Topics in MDPI journals

Dr. Mariia Dmitrenko

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Special Issue Information

Dear Colleagues,

Polymer membrane materials play a core role in membrane separation processes due to relative cheapness, ease of processing and possibility to adjust performance by various preparation and modification methods. Polymer membranes with tailored properties are of significant fundamental and industrial interest (in various fields of industry such as petrochemical, medical, pharmaceutical, food and others) due to the possibility to develop sustainable membrane processes which are so necessary for the modern society. Special emphasis will be placed on but not limited to the following:

membrane preparation
membrane characterization
bulk membrane modification
surface membrane modification
membrane transport properties in pressure-driven and diffusive membrane separation processes
membrane contactors
modeling/simulation of membrane processes

Dr. Anastasia Penkova
Dr. Tatiana Plisko
Dr. Mariia Dmitrenko
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Membranes is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

microfiltration
ultrafiltration
nanofiltration
gas separation
vapor permeation
pervaporation
composite membranes
mixed matrix membranes
hybrid membranes
membrane mass-transport
modeling/simulation
layer by layer
polyelectrolytes
plasma treatment
membrane contactors

Published Papers (10 papers)

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Research

28 pages, 6352 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Novel Thin Film Nanocomposite Membranes Based on Chitosan Succinate Modified with Fe-BTC for Enhanced Pervaporation Dehydration of Isopropanol

by Katsiaryna Burts, Tatiana Plisko, Mariia Dmitrenko, Andrey Zolotarev, Anna Kuzminova, Alexandr Bildyukevich, Sergey Ermakov and Anastasia Penkova

Membranes 2022, 12(7), 653; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes12070653 - 25 Jun 2022

Cited by 11 | Viewed by 2377

Abstract

The application of environmentally friendly and energy-efficient membrane processes allows improvement the ecological safety and sustainability of industrial production. However, the effective application of membrane processes requires novel high-performance thin film composite (TFC) membranes based on biopolymers to solve environmental problems. In this work for the first time novel thin film nanocomposite (TFN) membranes based on biopolymer chitosan succinate (ChS) modified with the metal organic framework iron 1,3,5-benzenetricarboxylate (Fe-BTC) were developed for enhanced pervaporation dehydration. The formation of a selective layer of TFN membranes on the porous membrane-support was carried out by two methods—dynamic technique and physical adsorption. The effect of the membrane formation method and Fe-BTC content in ChS layer on the structure and physicochemical properties of TFN membranes was investigated. The developed TFN ChS-based membranes were evaluated in the pervaporation dehydration of isopropanol (12–30 wt.% water). It was found that TFN ChS-Fe-BTC membranes prepared by two methods demonstrated improved permeation flux compared to the reference TFC ChS membrane. The best transport properties in pervaporation dehydration of isopropanol (12–30 wt.% water) were possessed by TFN membranes with 40 wt.% Fe-BTC prepared by dynamic technique (permeation flux 99–499 g m⁻² h⁻¹ and 99.99% water in permeate) and TFN membranes with 5 wt.% Fe-BTC developed by physical adsorption (permeation flux 180–701 g m⁻² h⁻¹ and 99.99% water in permeate). Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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13 pages, 2693 KiB

Open AccessEditor’s ChoiceArticle

Application of Cyclized Polyacrylonitrile for Ultrafiltration Membrane Fouling Mitigation

by Alexandra Pulyalina, Nadezhda Tian, Anna Senchukova, Ilya Faykov, Maria Ryabikova, Alexander Novikov, Natalia Saprykina and Galina Polotskaya

Membranes 2022, 12(5), 489; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes12050489 - 30 Apr 2022

Cited by 6 | Viewed by 2305

Abstract

In this study, novel composites were produced by blending partially cyclized polyacrylonitrile (cPAN) and poly(amide-imide) (PAI) in N-methylpyrrolidone in order to fabricate asymmetric membranes via phase inversion method. The compatibility of PAI and cPAN through possible intermolecular interaction was examined by quantum chemical calculations. The composite membranes were characterized by FTIR, SEM, contact angle measurements, etc. A considerable reduction in the contact angles of water and ethylene glycol (EG) was observed after adding cPAN to the PAI membrane, which is evidence of improved membrane hydrophilicity. Membrane transport properties were investigated in ultrafiltration tests by measuring the pure water flux, rejection of proteins, and flux recovery ratio (FRR). The best properties were found for the membrane containing 5 wt% cPAN; an increase in BSA rejection and a remarkable increase in FRR were observed, which can be explained by the hydrophilization of the membrane surface provided by the presence of cPAN. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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16 pages, 11403 KiB

Open AccessArticle

Removal of Humic Acid Using 3-Methacryloxypropyl Trimethoxysilane Functionalized MWCNT Loaded TiO₂/PES Hybrid Membrane

by Noor Fazliani Shoparwe, Lim-Cee Kee, Tunmise Ayode Otitoju, Hafiza Shukor, Nor’Izzah Zainuddin and Muaz Mohd Zaini Makhtar

Membranes 2021, 11(9), 721; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes11090721 - 21 Sep 2021

Cited by 9 | Viewed by 2172

Abstract

In the present work, a highly efficient mixed matrix membrane (MMM) for humic acid (HA) removal was developed. Multiwalled carbon nanotubes (MWCNTs) were functionalized in the presence of 3-methacryloxypropyl trimethoxysilane using the co-condensation method and were subsequently loaded with TiO₂ (prepared via the sol–gel route). The as-prepared material was then incorporated into a PES polymer solution to prepare a fMWCNT-TiO₂/PES hybrid membrane via non-solvent induced phase inversion. The microstructure of the membrane was characterized using Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscopy, water contact angle, thickness, porosity, and pore size. The fMWCNT-TiO₂/PES hybrid membrane was tested for the removal of HA and antifouling performance. The results show that the surface hydrophilicity of the membranes was greatly improved upon the addition of the fMWCNT-TiO₂ particles. The results show that 92% of HA was effectively removed after 1 h of filtration. In comparison with pristine membrane, the incorporation of fMWCNT-TiO₂ nanoparticles led to enhanced pure water flux (99.05 L/m² h), permeate flux (62.01 L/m² h), higher HA rejection (92%), and antifouling improvement (RFR: 37.40%, FRR: 86.02%). Thus, the fMWCNT-TiO₂/PES hybrid membrane is considered to be a great potential membrane for the improvement of ultrafiltration membranes. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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10 pages, 2071 KiB

Open AccessCommunication

Preparation and Desalination Performance of PA/UiO-66/PES Composite Membranes

by Dai Xuan Trinh, Ngo Nghia Pham, Patchanee Chammingkwan and Toshiaki Taniike

Membranes 2021, 11(8), 628; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes11080628 - 16 Aug 2021

Cited by 5 | Viewed by 2935

Abstract

UiO-66 nanoparticles are considered highly potential fillers for the application in desalination membranes. In this study, UiO-66 nanoparticles were anchored to PES membrane substrates, which were subsequently subjected to the interfacial polymerization reaction to coat a layer of polyamide (PA) on their surface. For comparison, a blank membrane incorporating no UiO-66 and a reference membrane incorporating ZrO₂ (instead of UiO-66) were prepared. All prepared membranes were tested for their desalination performance. The membranes containing UiO-66 were found to outperform the blank and the reference counterparts. The reason for this outperformance is possibly attributed to the hydrophilicity of UiO-66 nanoparticles and the presence of nanochannels in their structure. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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19 pages, 19112 KiB

Open AccessArticle

Express Method of Preparation of Hollow Fiber Membrane Samples for Spinning Solution Optimization: Polysulfone as Example

by Tatyana Anokhina, Alisa Raeva, Sergey Makaev, Ilya Borisov, Vladimir Vasilevsky and Alexey Volkov

Membranes 2021, 11(6), 396; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes11060396 - 27 May 2021

Cited by 11 | Viewed by 3977

Abstract

This article describes a new technique for the preparation of hollow fiber (HF) membrane samples using an automatic manipulator unit. The manipulator uses a syringe needle to form a HF of a given geometry. The needle in automatic mode is sequentially immersed, first into the polymer solution and then into the coagulation bath. The possibility of using a manipulator to obtain HF samples was studied on the known polysulfone (PSf)/N-methylpyrrolidone (NMP)/pore-forming additive system. A series of HF membrane samples were made within 29 h from twelve 1 mL PSf casting solutions. This was 15 times faster than obtaining samples of HF membranes at the multifunctional research laboratory facility. From the point of view of the consumption of the components of the casting solution, the use of the manipulator was 30 times more economical, and the consumption of water for precipitation and washing was 8000 times less. The developed method made it possible to study samples of HF by scanning electron microscopy (SEM), ultrafiltration, and evaluate its mechanical properties without spinning the membranes. Using the new technique, the optimal composition of the casting solution for the wet spinning of HF PSf membranes was selected during two weeks. Thus, the manipulator makes it possible to significantly reduce the time of the new membrane preparation, reduce the volume of used polymer, and thus makes it promising to study expensive or new membrane materials. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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29 pages, 4550 KiB

Open AccessArticle

Modification Approaches to Enhance Dehydration Properties of Sodium Alginate-Based Pervaporation Membranes

by Mariia Dmitrenko, Vladislav Liamin, Anna Kuzminova, Erkki Lahderanta, Nikolay Solovyev and Anastasia Penkova

Membranes 2021, 11(4), 255; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes11040255 - 01 Apr 2021

Cited by 14 | Viewed by 2638

Abstract

Transport characteristics of sodium alginate (SA) membranes cross-linked with CaCl₂ and modified with fullerenol and fullerene derivative with L-arginine for pervaporation dehydration were improved applying various approaches, including the selection of a porous substrate for the creation of a thin selective SA-based layer, and the deposition of nano-sized polyelectrolyte (PEL) layers through the use of a layer-by-layer (Lbl) method. The impacts of commercial porous substrates made of polyacrylonitrile (PAN), regenerated cellulose, and aromatic polysulfone amide were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), standard porosimetry method, and water filtration. The effects of PEL combinations (such as poly(sodium 4-styrene sulfonate) (PSS)/SA, PSS/chitosan, PSS/polyacrylic acid, PSS/poly(allylamine hydrochloride)) and the number of PEL bilayers deposited with the Lbl technique on the properties of the SA and SA/fullerene derivative membranes were studied by SEM, AFM, and contact angle measurements. The best characteristics were exhibited by a cross-linked PAN-supported SA/fullerenol (5%) membrane with five PSS/SA bilayers: permeation flux of 0.68–1.38 kg/(m²h), 0.18–1.55 kg/(m²h), and 0.50–1.15 kg/(m²h), and over 99.7, 99.0, and 89.0 wt.% water in the permeate for the pervaporation dehydration of isopropanol (12–70 wt.% water), ethanol (4–70 wt.% water), and tetrahydrofuran (5.7–70 wt.% water), respectively. It was demonstrated that the mutual application of bulk and surface modifications essentially improved the membrane’s characteristics in pervaporation dehydration. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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24 pages, 6152 KiB

Open AccessArticle

Concentration Polarization Enabled Reactive Coating of Nanofiltration Membranes with Zwitterionic Hydrogel

by Patrick May, Soraya Laghmari and Mathias Ulbricht

Membranes 2021, 11(3), 187; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes11030187 - 09 Mar 2021

Cited by 9 | Viewed by 2562

Abstract

In this study, the bottleneck challenge of membrane fouling is addressed via establishing a scalable concentration polarization (CP) enabled and surface-selective hydrogel coating using zwitterionic cross-linkable macromolecules as building blocks. First, a novel methacrylate-based copolymer with sulfobetain and methacrylate side groups was prepared in a simple three-step synthesis. Polymer gelation initiated by a redox initiator system (ammonium persulfate and tetramethylethylenediamine) for radical cross-linking was studied in bulk in order to identify minimum (“critical”) concentrations to obtain a hydrogel. In situ reactive coating of a polyamide nanofiltration membrane was achieved via filtration of a mixture of the reactive compounds, utilizing CP to meet critical gelation conditions solely within the boundary layer. Because the feasibility was studied and demonstrated in dead-end filtration mode, the variable extent of CP was estimated in the frame of the film model, with an iterative calculation using experimental data as input. This allowed to discuss the influence of parameters such as solution composition or filtration rate on the actual polymer concentration and resulting hydrogel formation at the membrane surface. The zwitterionic hydrogel-coated membranes exhibited lower surface charge and higher flux during protein filtration, both compared to pristine membranes. Salt rejection was found to remain unchanged. Results further reveal that the hydrogel coating thickness and consequently the reduction in membrane permeance due to the coating can be tuned by variation of filtration time and polymer feed concentration, illustrating the novel modification method’s promising potential for scale-up to real applications. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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20 pages, 4267 KiB

Open AccessArticle

Fabrication and Physicochemical Study of B2SA-Grafted Poly(vinyl Alcohol)–Graphene Hybrid Membranes for Dehydration of Bioethanol by Pervaporation

by Prakash B. Kalahal, Akshay S. Kulkarni, Ashok M. Sajjan, T. M. Yunus Khan, Irfan Anjum Badruddin, Sarfaraz Kamangar, Nagaraj R. Banapurmath, Narasimha H. Ayachit, Manu L. Naik and Vijaykumar S. Marakatti

Membranes 2021, 11(2), 110; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes11020110 - 04 Feb 2021

Cited by 9 | Viewed by 2502

Abstract

Tetraethylorthosilicate (TEOS)-crosslinked poly(vinyl alcohol) (PVA) solution was prepared and treated with benzaldehyde 2 sulphonic sodium salt acid (B2SA) for sulfonation. Different contents of graphene were incorporated into B2SA-grafted PVA–TEOS hybrid membrane to improve the membrane stability, mechanical strength, and overall pervaporation performance of the membranes. Membranes were fabricated using the casting technique. Developed membranes were then analyzed for their physicochemical changes by means of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscope (SEM), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), contact angle analysis (CA), and mechanical strength. The lower d-spacing value observed in WAXD was evidence for the decreased inter-chain distance between the polymer chains. DSC exhibited the enhanced thermal stability of the developed membranes compared to the plane PVA membrane with enhancement in T_g value (106 °C), which was well above the pervaporation experimental temperature. Incorporation of graphene induced higher mechanical strength to the fabricated membranes. Further, the membranes were tested for the pervaporation separation of bioethanol. All the membranes were stable throughout the pervaporation studies, with M-2 G showing the total permeation flux of 11.66 × 10⁻² kg/(m² h) at 30 °C. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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22 pages, 34129 KiB

Open AccessArticle

Amphiphilic Poly(dimethylsiloxane-ethylene-propylene oxide)-polyisocyanurate Cross-Linked Block Copolymers in a Membrane Gas Separation

by Ilsiya M. Davletbaeva, Ilgiz M. Dzhabbarov, Askhat M. Gumerov, Ilnaz I. Zaripov, Ruslan S. Davletbaev, Artem A. Atlaskin, Tatyana S. Sazanova and Ilya V. Vorotyntsev

Membranes 2021, 11(2), 94; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes11020094 - 29 Jan 2021

Cited by 6 | Viewed by 2162

Abstract

Amphiphilic poly(dimethylsiloxane-ethylene-propylene oxide)-polyisocyanurate cross-linked block copolymers based on triblock copolymers of propylene and ethylene oxides with terminal potassium-alcoholate groups (PPEG), octamethylcyclotetrasiloxane (D₄) and 2,4-toluene diisocyanate (TDI) were synthesized and investigated. In the first stage of the polymerization process, a multiblock copolymer (MBC) was previously synthesized by polyaddition of D₄ to PPEG. The usage of the amphiphilic branched silica derivatives associated with oligomeric medium (ASiP) leads to the structuring of block copolymers via the transetherification reaction of the terminal silanol groups of MBC with ASiP. The molar ratio of PPEG, D₄, and TDI, where the polymer chains are packed in the “core-shell” supramolecular structure with microphase separation of the polyoxyethylene, polyoxypropylene and polydimethylsiloxane segments as the shell, was established. Polyisocyanurates build the “core” of the described macromolecular structure. The obtained polymers were studied as membrane materials for the separation of gas mixtures CO₂/CH₄ and CO₂/N₂. It was found that obtained polymers are promising as highly selective and productive membrane materials for the separation of gas mixtures containing CO₂, CH₄ and N₂. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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25 pages, 7213 KiB

Open AccessArticle

Modification of Polysulfone Ultrafiltration Membranes via Addition of Anionic Polyelectrolyte Based on Acrylamide and Sodium Acrylate to the Coagulation Bath to Improve Antifouling Performance in Water Treatment

by Tatiana V. Plisko, Alexandr V. Bildyukevich, Katsiaryna S. Burts, Tatiana A. Hliavitskaya, Anastasia V. Penkova, Sergey S. Ermakov and Mathias Ulbricht

Membranes 2020, 10(10), 264; https://0-doi-org.brum.beds.ac.uk/10.3390/membranes10100264 - 28 Sep 2020

Cited by 23 | Viewed by 3346

Abstract

Surface modification of polysulfone ultrafiltration membranes was performed via addition of an anionic polymer flocculant based on acrylamide and sodium acrylate (PASA) to the coagulation bath upon membrane preparation by non-solvent induced phase separation (NIPS). The effect of PASA concentration in the coagulant at different coagulation bath temperatures on membrane formation time, membrane structure, surface roughness, hydrophilic-hydrophobic balance of the skin layer, surface charge, as well as separation and antifouling performance was studied. Scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, contact angle and zeta potential measurements were utilized for membrane characterization. Membrane barrier and antifouling properties were evaluated in ultrafiltration of model solutions containing human serum albumin and humic acids as well as with real surface water. PASA addition was found to affect the kinetics of phase separation leading to delayed demixing mechanism of phase separation due to the substantial increase of coagulant viscosity, which is proved by a large increase of membrane formation time. Denser and thicker skin layer is formed and formation of macrovoids in membrane matrix is suppressed. FTIR analysis confirms the immobilization of PASA macromolecules into the membrane skin layer, which yields improvement of hydrophilicity and change of zeta potential. Modified membrane demonstrated better separation and antifouling performance in the ultrafiltration of humic acid solution and surface water compared to the reference membrane. Full article

(This article belongs to the Special Issue Development, Investigation and Application of Novel Polymer Membranes)

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