High Performance Polymeric Membranes Research Articles

Effects of polyvinylpyrrolidone additive on structures and properties of Poly(m-phenylene isophthalamide) hollow fiber membranes -experiment observation and computation approach

This study systematically investigates the effect of introduction of polyvinylpyrrolidone (PVP) used as a hydrophilic additive and its molecular weight change on the morphological, mechanical properties, and membrane performances of poly(m-phenylene isophthalamide) (PMIA) hollow fiber (HF) membranes prepared by dry-jet wet spinning method. The results of the morphological and mechanical properties clearly show an increased proportion of a sponge-like pore structure and an overall improvement in the mechanical properties of the PMIA HF membranes with higher molecular weight PVP, respectively. Interestingly, molecular dynamics simulation showed that the presence of PVP within the PMIA matrix activated the overall movement of PMIA molecules, suggesting that the overall flexibility of the system, which can potentially inhibit the collapse of relatively brittle membranes, is increased by the presence of PVP. Finally, as the molecular weight of PVP increases, a typical trade-off phenomenon is observed on PMIA HF membranes, where the water permeability decreases while the rejection rate increases. Based on these results, the findings on the influence of PVP additive and its potential as a reinforcing agent observed in this study through experimental analysis and computational approaches are expected to provide new insights into the development of high-performance polymeric HF membranes.

Machine Learning Guided Polyamide Membrane with Exceptional Solute-Solute Selectivity and Permeance.

Designing polymeric membranes with high solute-solute selectivity and permeance is important but technically challenging. Existing industrial interfacial polymerization (IP) process to fabricate polyamide-based polymeric membranes is largely empirical, which requires enormous trial-and-error experimentations to identify optimal fabrication conditions from a wide candidate space for separating a given solute pair. Herein, we developed a novel multitask machine learning (ML) model based on an artificial neural network (ANN) with skip connections and selectivity regularization to guide the design of polyamide membranes. We used limited sets of lab-collected data to obtain satisfactory model performance over four iterations by introducing human expert experience in the online learning process. Four membranes under fabrication conditions guided by the model exceeded the present upper bound for mono/divalent ion selectivity and permeance of the polymeric membranes. Moreover, we obtained new mechanistic insights into the membrane design through feature analysis of the model. Our work demonstrates a ML approach that represents a paradigm shift for high-performance polymeric membranes design.

Proton Exchange Membrane Fuel Cells (PEMFCs): Advances and Challenges.

The study of the electrochemical catalyst conversion of renewable electricity and carbon oxides into chemical fuels attracts a great deal of attention by different researchers. The main role of this process is in mitigating the worldwide energy crisis through a closed technological carbon cycle, where chemical fuels, such as hydrogen, are stored and reconverted to electricity via electrochemical reaction processes in fuel cells. The scientific community focuses its efforts on the development of high-performance polymeric membranes together with nanomaterials with high catalytic activity and stability in order to reduce the platinum group metal applied as a cathode to build stacks of proton exchange membrane fuel cells (PEMFCs) to work at low and moderate temperatures. The design of new conductive membranes and nanoparticles (NPs) whose morphology directly affects their catalytic properties is of utmost importance. Nanoparticle morphologies, like cubes, octahedrons, icosahedrons, bipyramids, plates, and polyhedrons, among others, are widely studied for catalysis applications. The recent progress around the high catalytic activity has focused on the stabilizing agents and their potential impact on nanomaterial synthesis to induce changes in the morphology of NPs.

PEG functionalized graphene oxide-silver nano-additive for enhanced hydrophilicity, permeability and fouling resistance properties of PVDF-co-HFP membranes

In this study, polyethylene glycol (PEG) functionalized graphene oxide-silver nanocomposite (PEG-GOAg) was used as an effective nano-additive to enhance the hydrophilicity, permeability and antifouling resistance of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) support membrane. PEG-GOAg was synthesized by in-situ reduction of GO nanosheets with AgNO3 followed by covalent PEGylation reaction. PEG-GOAg active layer based PVDF-co-HFP membranes were then fabricated by resin infiltration method. Water contact angle of pristine membrane decreased effectively from 115.02° to 38.77° upon PEG-functionalization (1 PEG-GOAg-P). PEG-GOAg loading enhanced the hydrophilicity, permeability, porosity and antifouling properties of pristine membrane by up to 1 wt% due to intercalation of PEG chains on GOAg nanostructure. Water flux capacity of Pristine-P and GOAg-P membranes exhibited lower flux values with 216 and 564 Lm−2 h−1, respectively as compared with that of 1 PEG-GOAg-P membrane, which increased to 906 Lm−2 h−1. The 1 PEG-GOAg-P membrane also showed highest flux recovery ratio (91.3%) and BSA protein rejection rate (95.1%). Further, irreversible fouling ratio was lower with 1 PEG-GOAg-P (Rir ˜8.6%) as compared with pristine (49.1%) and 1 GOAg-P (22.8%) membranes, which demonstrated the high water permeability performance of 1 PEG-GOAg-P membrane. The presented study offers a great potential to optimize quality and cost in fabrication of high-performance polymeric nanocomposite membranes for a wide range of industrial ultrafiltration applications.

High pressure pure- and mixed sour gas transport properties of Cardo-type block co-polyimide membranes

Multi-block co-polyimides 6FDA-CARDO/6FDA-Durene with varying segmental lengths were synthesized and pure and mixed sour gas transport properties through dense membranes were investigated as function of feed pressure, temperature and gas composition. Pure gas measurement indicated that block co-polyimide 6FDA-CARDO/6FDA-Durene (2500/2500) membrane exhibits high permeation properties and separation characteristics with CO2 permeability and CO2/CH4 selectivity of up to 239 barrer and 28 respectively. The block co-polyimide also showed excellent performance under harsh sour gas environment (i.e. high H2S content of up to 36 vol% and feed pressure of up to 55 bar for a gas mixture consisting of CO2, CH4, N2, C2H6 and H2S). At 36 vol% H2S, the membrane exhibits H2S permeability and H2S/CH4 selectivity of up to 275 barrer and 24 respectively. These values and separation performance exhibited by the co-polyimide are comparable and very competitive even, as compared to the values obtained in some of the high performance polymeric membranes that have been reported in the literature. The stability of the block co-polyimide 6FDA-CARDO/6FDA-Durene membrane under these aggressive environments is quite impressive.

Cardo-type random co-polyimide membranes for high pressure pure and mixed sour gas feed separations

A series of aromatic random co-polyimide membranes based on 6FDA-Durene/CARDO backbone with varying content of CARDO moiety (3:1; 1:1 and 1:3) were synthesized for enhanced acid gas separation performance. Gas transport properties of pure and mixed gas streams consisting of H2S, CO2, He, CH4, N2 and C2H6 through the dense films of the co-polyimide were studied. Mixed sweet gas tests were done with feeds containing no H2S up to 55bar, while mixed sour gas measurements were conducted with feeds containing H2S up to 34bar for 10% H2S and 20% H2S. The membranes exhibit very attractive pure gas transport properties, as CO2 permeability and CO2/CH4 selectivity are up to 323 barrer and 35 respectively. Furthermore, the transport properties of sour gas mixture consisting of five gases were also found attractive, as the CO2/CH4 and H2S/CH4 ideal selectivities are in the range of 18–23 and 19–21 respectively; while CO2 and H2S permeabilities are in the range of 38–51 and 40–47 barrers respectively for 20% H2S in the gas mixture. These values and separation performance exhibited by the co-polyimide are comparable and very competitive even, as compared to the values obtained in some of the high performance polymeric membranes that have been reported in the literature. The stability of the random co-polyimide 6FDA-Durene/CARDO membrane under these aggressive environments is quite remarkable.

Modeling and Optimization of High-Performance Polymer Membrane Reactor Systems for Water–Gas Shift Reaction Applications

In production of electricity from coal, integrated gasification combined cycle plants typically operate with conventional packed bed reactors for the water-gas shift reaction, and a Selexol process for carbon dioxide removal. Implementation of membrane reactors in place of these two process units provides advantages such as increased carbon monoxide conversion, facilitated CO2 removal/sequestration and process intensification. Proposed H2-selective membranes for these reactors are typically of palladium alloy or ceramic due to their outstanding gas separation properties; however, on an industrial scale, the cost of such materials may become exorbitant. High-performance polymeric membranes, such as polybenzimidazoles (PBIs), present themselves as low-cost alternatives with gas separation properties suitable for use in such membrane reactors, given their significant thermal and chemical stability. In this work, the performance of a class of high-performance polymeric membranes is assessed for use in integrated gasification combined cycle (IGCC) units operated with carbon capture, subject to constraints on equipment and process streams. Several systems are considered for use with the polymeric membranes, including membrane reactors and permeative stage reactors. Based upon models developed for each configuration, constrained optimization problems are formulated which seek to more efficiently employ membrane surface area. From the optimization results, the limiting membrane parameter for achieving all carbon capture and H2 production specifications for water–gas shift reactor applications is determined to be the selectivity, α H 2 / C O 2, and thus a minimum value of this parameter which satisfies all the constraints is identified for each analyzed configuration. For a CO2 capture value of 90%, this value is found to be α = 61 for the membrane reactor and the 3-stage permeative stage reactor and α = 62 for the 2-stage permeative stage reactor. The proposed systems approach has the potential to be employed to identify performance limitations associated with membrane materials to guide the development of future polymeric and other advanced materials with desired membrane characteristics for energy and environmental applications.

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates.

High-performance polymeric membranes for gas separation are attractive for molecular-level separations in industrial-scale chemical, energy and environmental processes. Molecular sieving materials are widely regarded as the next-generation membranes to simultaneously achieve high permeability and selectivity. However, most polymeric molecular sieve membranes are based on a few solution-processable polymers such as polymers of intrinsic microporosity. Here we report an in situ cross-linking strategy for the preparation of polymeric molecular sieve membranes with hierarchical and tailorable porosity. These membranes demonstrate exceptional performance as molecular sieves with high gas permeabilities and selectivities for smaller gas molecules, such as carbon dioxide and oxygen, over larger molecules such as nitrogen. Hence, these membranes have potential for large-scale gas separations of commercial and environmental relevance. Moreover, this strategy could provide a possible alternative to 'classical' methods for the preparation of porous membranes and, in some cases, the only viable synthetic route towards certain membranes.

Thermal analysis and its application in evaluation of fluorinated polyimide membranes for gas separation

Seven polyimides based on (4,4′-hexafluoroisopropylidene) diphthalic anhydride, 6FDA, with different chemical structures were synthesized in a single pot two-step procedure by first producing a high molecular weight polyamic acid (PAA), followed by reaction with acetic anhydride to produce polyimide (PI). The resulting polymers were characterized using thermal analysis techniques including TGA, derivative weight analysis, TGA–MS, and DSC. The decarboxylation-induced thermal cross-linking, ester cross-linking through a diol, and ion-exchange reactions of selected polyimide membranes were investigated. Cross-linking of polymer membranes was confirmed by solubility tests and CO2 permeability measurements. The thermal analysis provides simple and timesaving opportunities to characterize the polymer properties, the ability to optimize polymer cross-linking conditions, and to monitor polymer functionalization to develop high performance polymeric membranes for gas separations.

Hydrogen separation and purification in membranes of miscible polymer blends with interpenetration networks

This study demonstrates the successful implications of blending technique cum chemical modification for the fabrication of high performance polymeric membranes for gas separation applications. The effect of variation in composition on miscibility and microstructure, gas permeability and selectivity of blend membranes is investigated. It is found that augmentation in PBI composition results in enhancement in gas separation performance of membranes which is attributed mainly to the effect of diffusivity selectivity. Analysis of the microstructure of membranes confirms the variations in chain packing density, d-spacing and segmental mobility of polymer chains as a result of blending. Separation performance of membranes is further ameliorated through chemical modification of blend constituents. Modification of PBI phase with p-xylene dichloride brings about slight improvements in selectivity performance, especially for H2/CO2 and H2/N2. In contrast, the selectivity of membranes is improved significantly after cross-linking of Matrimid phase with p-xylene diamine. The results indicate that higher tendency of Matrimid toward cross-linking reaction contributes more in controlling the transport properties of membranes through diffusion coefficient by increase in chain packing density and diminishing the excess free volumes. Results obtained in this study reveal the promising features of developed membranes for gas separation applications with great potential for hydrogen separation and purification on industrial scale.

Preparation and Performance of Polysulfone‐Cellulose Acetate Blend Ultrafiltration Membrane

In the development of high performance polymeric membranes, it is essential to design the molecular and morphological characteristics for specific applications. Polysulfone and cellulose acetate of blend membranes with various concentration of polymer pore former, PEG600 were prepared by phase inversion technique and used for ultrafiltration. Polymer blend composition, additive concentration, and casting conditions were optimized. The blend membranes were characterized in terms of compaction, pure water flux, water content, hydraulic resistance and separation of dextran studies. Surface morphology of the embranes was analyzed using scanning electron microscopy at different magnifications. Further, the characterized membranes were attempted for treatment of distillery effluents after secondary treatment and the results are discussed in detail.

Molecular and Morphological Designs of High Performance Polymeric Membranes

Currently, membrane separation techniques, such as reverse osmosis and ultrafiltration, play an important role in industrial separation technology. To develop high performance polymeric membranes, it is essential to design the molecular and morphological structures of the membranes for their specific applications. In the reverse osmosis field, we have developed several kinds of composite membranes for specific uses. Applications include ultrapure water production, seawater desalination, softening and desalination of brackish water, and recovery of valuable substances. In the course of development, thin-film composite membrane materials and membrane morphology have been analyzed intensively and are becoming clearer. These results enable us to control membrane performance by an optimum combination of membrane materials and membrane morphology. The morphological structure and chemical structure of the composite membranes were designed to optimize the performance of both the ultrathin layer and the supporting...