Hollow Fiber Membrane Research Articles

Heparin-modified polyether ether ketone hollow fiber membrane with improved hemocompatibility and air permeability used for extracorporeal membrane oxygenation

To expand the selection of raw material for fabricating extracorporeal membrane oxygenation (ECMO) and promote its application in lung disease therapy, polyether ether ketone hollow fiber membrane (PEEK-HFM) with designable pore characteristics, desired mechanical performances, and excellent biocompatibility was selected as the potential substitute for existing poly (4-methyl-1-pentene) hollow fiber membrane (PMP-HFM). To address the platelet adhesion and plasma leakage issues with PEEK-HFM, a natural anticoagulant heparin was grafted onto the surface using ultraviolet irradiation. Additionally, to explore the substitutability of the heparin layer while considering cost and scalability, a heparin-like layer composed of copolymers of acrylic acid and sodium p-styrenesulfonate was also constructed on the surface of PEEK-HFM Even though the successful grafting of heparin and heparin-like layers on the PEEK-HFM surface reduced the pore parameters, improvements in surface hydrophilicity also prevented the platelet-adhesion phenomenon and improved the anticoagulant behaviour, making it a viable alternative for commercial PMP-HFMs in ECMO production. Furthermore heparin-modified and heparin-like modified PEEK-HFMs demonstrated similar performance, indicating that synthetic layers can effectively replace natural heparin. This study holds practical and instructive significance for future research and the application of membranes in the development of oxygenators.

Flexible inner surface of polysulfone membranes prevents platelet adhesive protein adsorption and improves antithrombogenicity in vitro.

We investigated whether the condition of the inner surface of hollow fibers affects the blood compatibility of hemodialyzers. We used scanning probe microscope/atomic force microscopy (SPM/AFM) to investigate the height of the swelling and flexible layers (thickness and softness) on the inner surfaces of the hollow fibers. Next, we tested the blood compatibility between dialyzers comprising a hollow fiber membrane, in which the other dialyzers, except for PVP, were additionally coated using PS membranes coated with other materials. After blood was injected into the dialyzer and plugged, dynamic stimulation was performed by slightly rotating the dialyzer for 4 h, although there was no blood circulation. The vitamin E-coated polysulfone (PS) membrane showed a higher thickness and softness of the flexible layer than the asymmetric cellulose triacetate membrane without polyvinylpyrrolidone (PVP) and the PS membranes with PVP. We found that the dialyzer with vitamin E coating significantly suppressed the decrease in platelets, increase in β-TG, and increase in PF4 compared to those coated with NV polymer. Additionally, as the adsorbed protein on the inner surface, the total protein, fibronectin, and vWF levels were significantly lower in the vitamin E-coated dialyzer. The thickness and softness of the flexible layer of the inner surface of the hollow fiber membrane in vitro affect differences in blood coagulation performance in clinical research. Future clinical trials are required to confirm our results.

The change in thermal-induced interchain distance boosts the gas barrier property of PEI-derived hollow fiber membranes

In order to fulfill diverse special applications (e.g. food packaging, anticorrosion coatings, flame retardant coatings, biomedical industry and lighter-than air applications), the superior gas barrier property is principal requirement. Based on previous researches, the gas barrier property of membranes could be improved to some extent by changing their component, chemical structure, physical property, fabrication parameters or incorporating impermeable fillers. The above-mentioned approaches provide the enhanced gas barrier property owing to increment in resistance for diffusion of tested gas. That implies the intrinsic factors of the membrane such as free volume fraction of membrane are determined effect on permeability to gas. Accordingly, present work investigated the impact of thermal treatment on enhancement of gas barrier property by manipulating the temperature in the range of 200 °C to 240 °C to adjust the orientation of molecular structure. Based on a series of analysis as well as pure gas measurement, the hydrogen permeability of as-treated membrane decreased by almost 2700 times than that of neat membrane, which is due to the absence of amorphousity. The exceptional gas barrier properties of resultant membrane exhibited great potential for special applications and paved the feasible way for other amorphous precursor to prepare the gas barrier membrane.

Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi-Purpose Polyamine Functionalization.

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10-30nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm2 and GO layer thicknesses of ≈500nm are fabricated, and they exhibited a stable dye water permeance of 75 L m-2 h-1 bar-1, rejection of >99.5% for Direct red and Congo red, and Na2SO4/dye separation factor of 300-500, superior to state-of-the-art commercial membranes. The versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

Long-term operation of a full-scale membrane bioreactor for industrial wastewater treatment using polyvinyl fluoride hollow fiber membranes: A systematic evaluation during 18-year operation

A membrane bioreactor (MBR) is a robust, high-performance technology for wastewater treatment that has been commercialized and disseminated worldwide since 1990. Despite broad implementation of this technology in the wastewater sector, ultralong operation beyond the membrane lifetime has rarely been reported. Therefore, the objectives of this study were to investigate (1) the effectiveness of a manually-operated feedback strategy to prevent membrane biofouling by dosing with sodium hypochlorite and oxalic acid and (2) the organic carbon removal of industrial wastewater treated by a full-scale MBR system in a chemical plant. The manually-operated feedback strategy consisted of monitoring the transmembrane pressure (TMP) by a test module in a bench-scale MBR to detect an inflection point, that is, the point (15 kPa) at which the TMP switched from growing gradually to exponentially in time. Biocake formation became noticeable at the inflection point, suggesting the TMP at which the membrane should be chemically washed to prevent severe biofouling. A full-scale MBR system was installed with a polyvinylidene fluoride (PVDF) membrane for organic carbon removal. The membrane was washed with 3000 mg/L of sodium hypochlorite and 1 wt% oxalic acid when the TMP reached 15 kPa during operation. The MBR was successfully operated for over 18 years without the PVDF membrane being damaged or compromised by biofouling. Characterization of the foulants on the membrane surface revealed that membrane washing removed inorganic (calcium and iron) and organic (acid amides and polysaccharides) foulants, plausibly by the action of oxalic acid and sodium hypochlorite, respectively. Installing a robust PVDF membrane and performing chemical washing at an inflection point in the TMP dynamics enabled ultralong MBR operation beyond the regular membrane lifetime. The implementation of the advocated strategy paves the way for the low CO2 footprint operation of a PVDF MBR, which does not require frequent membrane replacement and laborious membrane ex-situ cleaning.

A high-throughput sample preparation approach for the determination of nonsteroidal anti-inflammatory drugs in urine samples through membrane-based microextraction employing a green supramolecular solvent

Nonsteroidal anti-inflammatory drugs (NSAIDs) are a class of drugs with antipyretic, analgesic, and anti-inflammatory effects widely used worldwide. This study aimed at developing an environmentally friendly and high-throughput sample preparation method for the determination of six NSAIDs in urine samples followed by high-performance liquid chromatography coupled to diode-array detection (HPLC-DAD). The experimental workflow consisted of hollow-fiber microporous membrane liquid-liquid extraction (HF-MMLLE) using a supramolecular solvent immobilized into the porous of polypropylene hollow membranes (1 cm length). These membranes were attached to a 96-well plate system to permit multiple extractions simultaneously. Under the optimized conditions, limits of detection (LODs) and limits of quantification (LOQs) ranged from 6.06 to 30.3 µg/L and from 20 to 100 µg/L, respectively. The linear ranges varied from 20 to 1000 µg/L for indomethacin and diclofenac, from 50 to 1000 µg/L for ketoprofen and ibuprofen, and from 100 to 1000 µg/L for naproxen and fenoprofen. The coefficients of determination (R²) ranged from 0.9735 to 0.9997. Intraday precision ranged from 6.13 to 20.11 %, interday precision varied from 2.87 to 20.72 %, and accuracy ranged from 92.49 to 126.89 %. Moreover, the recently proposed Sample Preparation Metric of Sustainability (SPMS) was employed to evaluate the greenness of the sample preparation technique resulting in a score of 8.0, which is highly satisfactory according to the concepts of green analytical chemistry.

Preparation of high-performance PVDF hollow fiber microporous membranes via the c-TIPS process with water-insoluble solvent as the second solvent

Triethyl phosphate (TEP) is a promising solvent for the c-TIPS process given its high boiling point and water miscibility. However, casting solutions containing high TEP concentration generally trigger gelation, giving a dense outer surface in PVDF membrane. In this work, we fabricated PVDF hollow fiber membranes with a porous outer surface and excellent mechanical strength via a complex thermally induced phase separation (c-TIPS) method and applied them in the DCMD process. A water-insoluble solvent, dibasic ester solvents (DBEs), was used as the second solvent to modulate the phase separation process of the PVDF/TEP system. The mass transfer between the coagulation bath and the DBEs solvent was analyzed. It could decrease the polymer-solvent interactions and the rate of solvent efflux in the coagulation bath, contributing to the development of a porous membrane structure. When the weight ratio of TEP/DMA was 1, the optimized PVDF hollow fiber membrane exhibited a tensile strength of 8.34 MPa, an average pore diameter of 0.14 μm, giving the permeate flux of 18.56 ± 2.5 kg m−2 h−1 in DCMD and excellent operational stability when subjected to high brine concentration. Thus, the fabrication method shows a promising potential for tailoring the surface porosity and bulk structure. The PVDF membranes developed in this study demonstrate potential for use in membrane distillation and related applications.

Exploring Electrochemistry: A Self-Designed Experiment by Students for Electrochemical Impedance Spectroscopy Measurement of Hollow Fiber Membranes

Exploring Electrochemistry: A Self-Designed Experiment by Students for Electrochemical Impedance Spectroscopy Measurement of Hollow Fiber Membranes

Effect of microwave treatment on morphological and separation characteristics of polysulfone hemodialysis hollow fiber membranes

Effect of microwave treatment on morphological and separation characteristics of polysulfone hemodialysis hollow fiber membranes

Insights on influence of polymer molecular weight on gas sorption, transport and plasticization in glassy 6FDA-DAM polyimide membranes

It is well-known that spinning of defect-free asymmetric polyimide hollow fibers is promoted by using high polymer molecular weight. On the other hand, effects of polymer molecular weight on microstructure and separation performance of dense film 6FDA-based polyimide membranes relevant to sheath layers of composite membranes are less well-explored. In this work, gas sorption, diffusion and permeation of CO2, N2 and CH4 for 6FDA-DAM dense films are considered for 45 kDa and 176 kDa weight average molecular weights. Such molecular weights are relevant for practical hollow fiber spinning of membranes. Earlier results for polystyrene samples show similar trends in dual mode sorption model results like those noted here for the 6FDA-DAM polyimide case; however, effects on permeation like those considered here were not addressed for the polystyrene case. Here we also address actual pure and mixed gas CO2 and CH4 permeation and show higher free volumes, higher gas permeability but lower 50:50 CO2/CH4 selectivity associated with the higher molecular weight sample. Analysis using the self-consistent dual-mode sorption and transport models help understand the observed trends. Our results suggest denser packing of polymer segments exists in the Henry's law environment of the low molecular weight sample. Moreover, the higher polymer segmental packing in the Henry's law environment suppresses CO2 plasticization with a dual-mode microstructure controlling separation performance and plasticization behavior for this important member of the 6FDA polyimide family. We show evidence of effects of charge transfer complexes as possible main features in these trends. These dense film results help guide future work on dense sheath layers on composite hollow fiber membranes.

Mass transfer of bilirubin and bovine serum albumin in hollow fiber membrane module of artificial liver

Understanding the mass transfer behaviors in hollow fiber membrane module of artificial liver is important for improving toxin removal efficiency. A three-dimensional numerical model was established to study the mass transfer of small molecule bilirubin and macromolecule bovine serum albumin (BSA) in the hollow fiber membrane module. Effects of tube-side flow rate, shell-side flow rate, and hollow fiber length on the mass transfer of bilirubin and BSA were discussed. The simulation results showed that the clearance of bilirubin was significantly affected by both convective and diffusive solute transport, while the clearance of macromolecule BSA was dominated by convective solute transport. The clearance rates of bilirubin and BSA increasd with the increase of tube-side flow rate and hollow fiber length. With the increase of shell-side flow rate, the clearance rate of bilirubin first rose rapidly, then slowly rose to an asymptotic value, while the clearance rate of BSA gradually decreased. The results can provide help for designing structures of hollow fiber membrane module and operation parameters of clinical treatment.

Investigation on the synthesis conditions of poly(4-methyl-1-pentene) hollow fiber membrane with high gas permeability and strong tensile strength

Investigation on the synthesis conditions of poly(4-methyl-1-pentene) hollow fiber membrane with high gas permeability and strong tensile strength

Performance enhancement of hollow fiber membrane contactors for CO2 absorption using MEA-based functionalized nanofluids

Performance enhancement of hollow fiber membrane contactors for CO2 absorption using MEA-based functionalized nanofluids

Desalination Performance Evaluation of hBN@UiO‐66 MOF Incorporated Hollow Fiber Membrane using Membrane Distillation

AbstractIn the present study, the polyvinylidene fluoride (PVDF) modified hollow fiber (HF) membranes have been synthesized by dry‐jet wet phase inversion technique for desalination via direct contact membrane distillation (DCMD). UiO‐66 metal‐Organic framework (MOF) and surface‐modified UiO‐66 with h‐BN nanomaterial have been incorporated with PVDF‐HF membrane. The various analytical methods like FE‐SEM, FTIR, PXRD, TGA, tensile strength, were used to characterize prepared MOF and HF membranes. It was observed from DCMD results that the h‐BN@UiO‐66/PVDF (M3) HF membrane gives higher flux than UiO‐66/PVDF (M2) and pure PVDF (M1) membrane. In the present investigation, response surface methodology (RSM) by box‐behnken design (BBD) was used to optimize the DCMD system and evaluate the behavior of operating parameters such as feed temperature, feed concentration, and feed flow rate. The optimum operating values of feed temperature, feed flow rate, and feed concentration were found as 65 °C, 1 LPM, and 1.5 wt.%, respectively. Under optimum conditions, the M3 HF membrane gives the highest flux of 26.78 L/m2 ⋅ h compared to M2 and M1 membranes. During DCMD, salt rejection is almost greater than 99.8 % for all prepared membranes. Other salts like potassium chloride (KCl), Magnisium Sulphate (MgSO4), and calcium sulphate (CaSO4) are also used to check salt rejection of all membranes at optimum operating conditions. Moreover, the M3 membrane exhibits stable permeate flux and high salt rejection (>99.9 %) at optimized process parameters over 80 h running. Overall, the present study provides the positive effects of h‐BN nanoparticles and UiO‐66 MOF on HF membrane to improve performance in DCMD.

Jet-assisted membrane filtration and design application: A model for fouling removal area estimation

Membrane fouling remains a significant challenge in desalination and other membrane-based filtration processes. This study presents a novel force-balance model to accurately estimate the de-fouling area in jet-assisted filtration for in-situ fouling control. The model includes various design parameters, such as initial jet velocity, nozzle diameter, impinging angle, membrane pore size, membrane resistance, and permeate flux. The validation showed a strong correlation between theoretical predictions and experimental observations, with an R2 value of 0.97, indicating high predictive accuracy. Additionally, an empirical formula and design automation tools were developed to facilitate the configuration of jet filtration modules, enabling practical application of the findings. As a demonstration, the arrangement of multiple jets in a hollow fiber membrane module was optimized using the model, significantly improving microalgae filtration performance. The optimized jet configuration enhanced permeate flux by 236 % and reduced the specific energy consumption by 67 % compared to conventional setups. This research offers a framework for extending the application of jet-based fouling mitigation and cleaning in various membrane filtration systems, providing substantial improvements in efficiency and operational sustainability.

Comprehensive analysis of polysulfone membrane humidifier in hydrogen fuel cell vehicles: Experimental and theoretical approaches

This study performed a comprehensive experimental and theoretical analysis of a shell-and-tube type gas-to-gas humidifier module in a 95 kW class hydrogen fuel cell vehicle. The humidifier module features a polysulfone hollow fiber membrane characterized by its hydrophilic and non-fluorinated properties. Experimental investigations were conducted to understand the impacts of the inlet temperature, relative humidity, and temperature differences on heat and mass transfer rates, and the approach dew point temperature (ADT). The results showed that the ADT increased from 12.42 to 15.89 °C with a temperature difference of 15 °C between the shell and tube inlet sides, as the flow rate increased from 1000 to 3400 L/min, with the highest performance observed at lower flow rates. Simultaneously, a detailed theoretical model was developed, incorporating a new dual-mode sorption approach that accounts for temperature dependency within the solution-diffusion mechanism across the membrane. The developed model was in good agreement with the experimental results, with a relative error of less than 5 %. Furthermore, the dynamic model accurately predicts the response of the humidifier module to step changes in feed flow rates, simulating load variations in the fuel cell vehicle. This provides valuable insights into the humidifier's adaptability and responsiveness, which are crucial for optimizing its performance under various operating conditions.

Treatment of wastewater from oil palm industry in Malaysia using polyvinylidene fluoride-bentonite hollow fiber membranes via membrane distillation system

Membrane distillation (MD) is gaining increasing recognition within membrane-based processes for palm oil mill effluent (POME) treatment. This study aims to alter the physicochemical characteristics of polyvinylidene fluoride (PVDF) membranes through the incorporation of bentonite (B) at varying weight concentrations (ranging from 0.25 wt% to 1.0 wt%). Characterization was conducted to evaluate changes in morphology, thermal stability, surface characteristics and wetting properties of the resulting membranes. The resulting membranes were also tested using direct contact membrane distillation (DCMD) with POME as the feed solution, aiming to generate high-purity water. Results indicated that the PVDF-0.3B and PVDF-0.5B membranes achieved the highest water vapor flux. The finger-like structure and macrovoids present in these membranes aid in minimizing mass resistance during vapor transport and enhancing permeate flux. All membranes demonstrated exceptional performance in removing contaminants, eliminating total dissolved solids (TDS) and achieving over 99% rejection of chemical oxygen demand (COD), nitrate nitrogen (NN), color, and turbidity from the feed solution. The permeate water analysis showed that the PVDF-0.3B membrane had superior removal efficiency and met the standards set by the local Department of Environment (DOE). The PVDF-0.3B membrane was chosen as the preferred option because of its consistent flux and high removal efficiency. This study demonstrated that incorporating bentonite into PVDF membranes significantly enhanced their properties and performance for POME treatment.

Construction of zwitterionic surface of PVDF hollow fiber membrane and the study on the mechanism of “autonomy-response” synergistic enhancement anti-fouling

In this study, polyvinylidene fluoride (PVDF)/styryl maleic anhydride (SMA) hollow fiber membrane was fabricated using the Thermally Induced Phase Separation (TIPS) technique. Subsequently, zwitterion-sulfobetaine methacrylate (SBMA) was introduced to the membrane surface through a Michael addition reaction to create a nearly electrically neutral membrane surface. This modification effectively mitigated the high adsorption of differently charged protein pollutants on the membrane surface, thereby enhancing its anti-fouling performance. Simultaneously, the membrane surfaces with positive and negative charges were separately constructed, and the impact of membrane surface charge properties on the anti-fouling performance against positively and negatively charged foulants was investigated. Furthermore, detailed studies were conducted on the chemical structure, surface morphology, performance, and anti-fouling mechanism of the modified membranes. The results indicate that the electrically neutral membrane modified by zwitterionic SBMA exhibited excellent anti-fouling properties against both bovine serum albumin (BSA) and lysozyme (LYZ), with a flux recovery rate (FRR) reaching 96.5 % and 94.6 %, respectively. The static adsorption capacities of BSA and LYZ on the membrane surface decreased to 5.89 μg cm−2 and 9.53 μg cm−2, respectively. Furthermore, the study investigated the structure of the hydration layer formed by zwitterionic SBMA on the membrane surface, as well as its hydration capacity and anti-fouling mechanism. Subsequently, through an assessment of the long-term stability of the modified membrane and its flux recovery rate (FRR), in conjunction with theories related to hydration layers and thermodynamics, it elucidated the anti-fouling mechanism involving “autonomy-response” synergistic enhancement of zwitterions. These findings will offer new strategies for researching hollow fiber membranes with superior anti-fouling properties and for applying zwitterions in membrane technology.

Effect of the main properties of membrane materials on denitrification of hydrogen-based membrane biofilm reactors (H2-MBfRs)

Hydrogen-based membrane biofilm reactors using hollow-fiber membrane modules as their functional cores can play an important role in treating oxidizing pollutants. However, most studies have focused on pollutant removal, and few have investigated how membrane material properties affect reactor's operation. Here, we selected polyvinyl chloride (PVC) and polyvinylidene fluoride (PVDF) hollow fiber membrane materials with large differences in membrane surface properties to assemble the reactor, and investigated how the membrane properties affected nitrate removal and EPS secretion in MBfRs. The results showed that the membrane surface zeta potential and membrane contact angle had a certain positive impact on the NO3−-N removal rate and total EPS secretion in the MBfRs. When the contact angle (74.51–85.51°) and zeta potential (−12.5–4.5) increased, the biofilm on the membrane surface secreted more binding proteins (90.81–113.54 mg/gVSS), facilitating reactor biofilm growth, pollutant removal, and impact loads. Moreover, the properties of the experimentally selected PVC membrane material are more suitable for MBfR operation and are in line with the fundamental need for energy saving and emission reduction in modern society. This study provides a theoretical basis for the selection of membrane materials to enhance denitrification in H2-MBfRs, and an engineering foundation for reactors applications.

Circular hybrid membrane process treating high-salinity ammonium-rich pharmaceutical wastewater

Ammonia-rich saline wastewater is a common byproduct of the pharmaceutical industry. Hollow fiber membrane contactors (HFMCs) show potential for NH3 recovery, enabling valuable product recycling. Our previous work indicated that excessive NaOH usage and increased salinity of the treated effluent are major setbacks when employing HFMCs for NH3 recovery from pharma wastewater. Therefore, finding alternative approaches to reduce chemical use and salinity is vital. This study demonstrates the integration of bipolar membrane electrodialysis (BMED) with HFMC for NH3 recovery, chemical recycling, and salinity reduction. This novel, highly circular concept was tested using real pharmaceutical wastewater. We varied the volume ratios between compartments to assess the BMED flexibility in attaining different treatment goals. BMED achieved over 90% salinity reduction and produced concentrated base and acid in all volume ratios tested, saving 70% of the NaOH required for pH increase before the HFMC step. The HFMC achieved over 98% NH3 recovery in two sets of five consecutive cycles, using either a BMED-generated base or NaOH. A preliminary economic analysis revealed a 47% reduction and 86% increase in expenses on chemicals and energy, respectively, compared to HFMC without BMED. Nevertheless, since the largest operating expense was the purchase of chemicals, integrating the BMED step reduced the overall operating expenses of the treatment by 33% (from $3.76 to $2.54 per kg N). The treated effluent’s quality allows discharge to conventional wastewater treatment plants, resulting in economic and environmental benefits. This work highlights the importance of innovative separation processes in advancing toward cleaner drug manufacturing.