The Role of Organically Modified Clay Particle on Thermal,Mechanical and Gas Barrier Properties of Polyimide Nanocomposites and Toward Improvement of Gas Selectivities

ABSTRACT

Novel mixed matrix membranes with various Cloisite®15A in polyimide (PI) matrix were developed for gas separation. The synthesized membranes were characterized by the FE-SEM, XRD, DTG and TEM. According to FE-SEM results, at 3 wt% of Cloisite®15A, the fillers were dispersed homogeneously in the PI polymer matrix. The tensile properties of PI/Cloisite®15A increased gradually with clay content. It was interesting to note that the pure gas selectivity was seen to be increased with decreasing the filler loading. At 1 wt% clay loading, PI/Cloisite®15A nanocomposites showed an increase of 55% in CO₂/CH₄ ideal selectivity over pristine PI membrane.     

Mixed matrix membranes of Pebax1657 loaded with iron benzene‐1,3,5‐tricarboxylate for gas separation

Mixed matrix membranes offer major advantages in gas separation processes due to desirable properties found in both organic and inorganic membranes. In this study, a novel mixed matrix membrane was prepared for such application by incorporating iron benzene‐1,3,5‐tricarboxylate (Fe‐BTC) into the poly(amide‐6‐b‐ethylene oxide) (Pebax1657) polymer. Membranes with various loadings of 5, 10, and 20 wt% Fe‐BTC in the polymer matrix were fabricated to investigate the effect of filler loading on the membrane performance. Membranes, prepared by solution‐casting were characterized by scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared, X‐ray diffraction, and tensile test. Pure gas separation of CO₂, CH₄, and N₂ and ideal gas selectivity of CO₂/CH₄ and CO₂/N₂ were performed and permeation tests were carried out under 4, 8, and 12 bar pressures. Results show that adding Fe‐BTC into the Pebax1657 matrix improved both permeability and selectivity of the filled membranes. For instance, 10 wt% loading of Fe‐BTC into the Pebax1657 matrix led to CO₂ permeability increase of 49% as well as CO₂/CH₄ and CO₂/N₂ selectivities enhancements of about 36% and 16%, respectively. POLYM. COMPOS., 38:1363–1370, 2017. © 2015 Society of Plastics Engineers     

Synthesis and characterization of rubbery/glassy blend membranes for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> gas separation

A series of blend membranes made from the rubbery polyether block amide (Pebax®1657) and a glassy polymer, polyethersulfone (PES) or Matrimid 5218, were fabricated by solution casting with different ratios (10–40 %), in order to combine high permeability of the former with high selectivity of the latter polymer for CO₂/CH₄ gas separation. The membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), and stress–strain tests. These blend membranes showed two distinct T _g s, indicating their immiscible nature as confirmed by SEM images. However, weak intermolecular interaction between polymers, as illustrated by the FTIR results, corresponds to some degree to their compatibility and improved mechanical strength, compared to the pure Pebax®. TGA analysis revealed that addition of glassy polymer improved membranes’ thermal stability. Effect of feed pressure on membrane separation, investigated by three different pressures (4, 8, and 12 bar), indicated increased permeability for higher pressures for both CO₂ and CH₄. Gas separation tests also pointed to improved separation properties of the blend membranes compared to those of the neat polymers, prepared the same way.     

ZIF-8 Filled Polydimethylsiloxane Membranes for Pervaporative Separation of n-Butanol from Aqueous Solution

ZIF-8-filled polydimethylsiloxane (PDMS) membranes, PDMS/ZIF-8, were prepared by a two-step polymerization process and were used to recover n-butanol from an aqueous solution by pervaporation (PV). Compared with pure PDMS membrane, PDMS/ZIF-8 membranes demonstrated an obviously higher n-butanol permselectivity. As an increase of ZIF-8 content, n-butanol/water selectivity increased initially and then decreased, while the n-butanol and water permeability decreased monotonously. PDMS/ZIF-8 membrane containing 2 wt% ZIF-8, that is, PDMS/ZIF-8-2 showed the highest selectivity. On the other hand, selectivity and permeability for n-butanol and water of PDMS/ZIF-8-2 membrane decreased with the increase of operating temperature. The selectivity and permeability for n-butanol reached 7.1 and 3.28 × 10⁵ barrer, respectively, at 30°C when the feed concentration of n-butanol was 0.96 wt%.     

Blends of Poly(ether imide) and Styrene Sulfonic Acid Based Polymer: Thermal,Mechanical and Ionic Conduction Behavior

Dense membranes based on poly(ether imide) (PEI) and poly(styrene sulfonic acid-co-maleic acid) (PSSAMA) was obtained by extrusion and compression molding. Blends with different PSSAMA content (1, 3, 5, and 10 wt%) were prepared. Their morphology was investigated by scanning electron microscopy (SEM) and their thermal properties by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic-mechanical analysis (DMA). Two glass transition temperatures (T_g) (100 and 216°C) appeared when high contents of PSSAMA were added to PEI, indicating that the polymers form an immiscible system. TGA curves showed that the first weight loss occurred above 400°C for all blends, indicating a good thermal stability. Water uptake measurements have shown that the membranes presented low swelling when compared with Nafion®. The proton conductivity of the membrane with 10 wt% of PSSAMA obtained bv impedance measurements was 0.006 × 10^?2 S·cm^?1.     

High speed spin coating in fabrication of Pebax 1657 based mixed matrix membrane filled with ultra-porous ZIF-8 particles for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation

Modified ultra-porous ZIF-8 particles were used to prepare novel ZIF-8/Pebax 1657 mixed matrix membranes (MMMs) on PES support for separation of CO₂ from CH₄ using spin coating method. TEM and SEM were used to characterize modified ZIF-8 particles. SEM was also used to investigate the morphology of synthesized MMMs. The MMMs with thinner selective layer showed higher CO₂ permeability and lower CO₂/CH₄ selectivity in permeation tests compared to MMMs with thicker selective layer. The plasticization was recognized as the main reason for rise in CO₂ permeability and drop in CO₂/CH₄ selectivity of thinner MMMs. The gas sorption results showed that the high permeability of CO₂ in MMMs is mainly due to the high solubility of this gas in MMMs, leading to high CO₂/CH₄ solubility selectivity for MMMs. The fractional free volume and void volume fraction of MMMs increased as the thickness of membrane decreased. Applying higher mixed feed pressures and permeation tests temperatures resulted in increase in CO₂ permeability and decrease in CO₂/CH₄ selectivity. At highest testing temperature (60 °C), the CO₂ permeability of synthesized MMMs with thinner selective layer remarkably increased.     

Effects of simultaneous chemical cross-linking and physical filling on separation performances of PU membranes

The novel modified polyurethane (PU) membranes were prepared by β-cyclodextrin (CD) cross-linking and SiO₂/carbon fiber filler, simultaneously. The structures, thermal stabilities, morphologies, and surface properties were characterized by FTIR, TGA, SEM, and contact angle. The results showed that the addition of inorganic particles increased the thermal stabilities of PU membranes. The modified PU membranes possessed more hydrophobic surfaces than pure PU. In the swelling investigation, PU and its modified membranes were swelled gradually with increasing phenol content in the mixture. The membranes modified by CD cross-linking (PUCD) demonstrated the highest swelling degree. Pervaporation (PV) performances were investigated in the separation of phenol from water. Three kinds of modified membranes obtained better permeability and selectivity than PU membranes. With the feed mixture of 0.5 wt% phenol at 60 °C, the modified PU membrane by CD cross-linking and SiO₂ filler (PUCD-S) obtained the total flux of 5.92 kg μm m^?2 h^?1 which was above doubled that of PU (2.90 kg μm m^?2 h^?1). The modified PU membrane by CD cross-linking and carbon fiber filling (PUCD-C) obtained the separation factor of 51.31 which was nearly tripled that of PU (17.72). The PUCD membranes showed both better permeability and selectivity than the pure PU membranes. The increased phenol content induced an increased separation factor of PUCD and PU, but a decreased selectivity of PUCD-S and PUCD-C. The methods of CD cross-linking and inorganic particle filling were effective to develop the overall separation performances, greatly.     

Polyurethane-SAPO-34 mixed matrix membrane for CO2/CH4 and CO2/N2 separation

SAPO-34 nanocrystals (inorganic filler) were incorporated in polyurethane membranes and the permeation properties of CO₂, CH_4, and N₂ gases were explored. In this regard, the synthesized PU-SAPO-34 mixed matrix membranes (MMMs) were characterized via SEM, AFM, TGA, XRD and FTIR analyses. Gas permeation properties of PU-SAPO-34 MMMs with SAPO-34 contents of 5 wt%, 10 wt% and 20 wt% were investigated. The permeation results revealed that the presence of 20 wt% SAPO-34 resulted in 4.45%, 18.24% and 40.2% reductions in permeability of CO_2, CH_4, and N₂, respectively, as compared to the permeability of neat polyurethane membrane. Also, the findings showed that at the pressure of 1.2 MPa, the incorporation of 20 wt% SAPO-34 into the polyurethane membranes enhanced the selectivity of CO₂/CH₄ and CO₂/N₂, 14.43 and 37.46%, respectively. In this research, PU containing 20 wt% SAPO-34 showed the best separation performance. For the first time, polynomial regression (PR) as a simple yet accurate tool yielded a mathematical equation for the prediction of permeabilities with high accuracy (R² > 99%).     

Fabrication of zeolitic imidazolate frameworks based mixed matrix membranes and mass transfer properties of C4H6 and N2 in membrane separation

1,3-Butadiene (BD) is a petrochemical-based volatile organic compound, extensively used for the manufacture of synthetic rubber. There is no method reported for its recovery from nitrogen mixture. Herein, for the first time, BD is efficiently recovered by gas separation through facile and novel mixed-metal ZIF-8 based mixed matrix membranes (MMMs). Addition of Ni-ZIF-8 nanoparticles in PDMS matrix, significantly improved the penetrant-membrane interactions and the solution-diffusion properties of BD. Positron annihilation lifetime spectroscopy analysis showed that the well dispersion of Ni-ZIF-8 in PDMS enhanced the free volume of membrane and created efficient continuous paths for BD diffusion. Then, 15 wt% Ni-ZIF-8 MMM exhibited the BD permeance of 323 GPU and the BD/N₂ ideal selectivity of 19.5, which were 60 and 81% higher than pure PDMS membrane, respectively. The simultaneous enhancement of BD permeance and BD/N₂ ideal selectivity indicated that Ni-ZIF-8 was an effective filler applied in MMMs for efficient BD recovery.     

Synthesis and characterization of LiBOB‐based PVdF/PVC‐TiO2 composite polymer electrolytes

Synthesis and characterization of composite polymer electrolytes based on lithium bis(oxalato)borate (LiBOB) and a host matrix of nanoparticulate anatase dispersed in phase‐separated poly(vinylidenefluoride) (PVdF)‐poly(vinylchloride) (PVC) are described. Ethylene carbonate (EC) and diethyl carbonate (DEC) were used as plasticizers in the membranes, and nanoparticulate TiO₂ (anatase) was used as the filler. The membranes were characterized by SEM, XRD, and a.c. impedance measurements. A membrane with 2.5 wt% filler exhibited a conductivity of 5.43 × 10^?4 S.cm^?1 at ambient temperature. Filler levels above 2.5 wt% increased the crystallinity of the membranes, rendering them less conducting. Activation energy and coherent length of the composite polymer electrolytes have also been calculated. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers.     

Performance evaluation of a synthesized and characterized Pebax1657/PEG1000/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> membrane for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation using response surface methodology

In this work, the response surface methodology (RSM) based on the central composite design (CCD) was used to examine effects of different gamma alumina (γ-Al₂O₃) loadings (0 to 8 wt.%) and various polyethylene glycol 1000 (PEG1000) contents (0 to 40 wt.%) as parameters on membrane preparation. Accordingly, pure carbon dioxide (CO₂) and methane (CH₄) gasses permeability and ideal CO₂/CH₄ selectivity values were considered as responses. Poly (ether block amide) 1657 (Pebax1657) was used as the base polymer matrix for the membranes fabrication. The neat Pebax1657 membrane was prepared via solution casting-solvent evaporation method and the other membranes were prepared via solution blending technique. Analysis of variance (ANOVA) was used to analyze the experiments statistically and the results indicated that the optimized amounts of γ-Al₂O₃ nanoparticles and PEG1000 in order to enhance both CO₂ permeability and ideal CO₂/CH₄ selectivity were 8 wt.% and 10 wt.%, respectively. Additionally, a comparison between the separation performance of the neat membrane, the nanocomposite membrane with the optimum amount of γ-Al₂O₃ nanoparticles, the blended membrane with optimum amounts of PEG1000, and the blended nanocomposite membrane with optimum amounts of γ-Al₂O₃ nanoparticles and PEG1000 was presented. The obtained gas permeation results showed that the blended nanocomposite membrane exhibits the highest CO₂/CH₄ separation performance compared to the neat Pebax membrane.     

Fast-current-driven synthesis of ultrathin ZIF-8 membrane on ceramic tube for propene/propane separation

MOF membranes are very promising in molecular separation, but it is still a challenge for industrial applications due to the complex and time-consuming synthesis. We use the fast current-driven synthesis (FCDS) method to achieve controlled growth of ZIF-8 membranes on porous graphite-coated ceramic tubes by controlling the growth time and current density. Grown for 30 min at a current density of 0.74 mA/cm², the ZIF-8 membrane exhibits selectivity for C₃H₆/C₃H₈ up to 63 with C₃H₆ permeance of 6 × 10⁻⁹ mol/(m² s Pa). Furthermore, the ZIF-8 membrane exhibits a pressure resistance of up to 3 bar and good stability of ~96 h. This work realizes the breakthrough of the MOF membrane synthesis via FCDS method from the frequently-used expensive and fragile anodic aluminum oxide (AAO) disc substrate to the tough ceramic tubular substrate, which broadens the road for the industrialization of MOF membranes in gas separation fields.     

Improved CO2/CH4 separation performance of mixed-matrix membrane by adding ZIF-7-NH2 nanocrystals

Membrane-based technology is an attractive alternative in terms of CO₂ separation. Pebax-based membranes are regarded as potential candidates for CO₂ separation due to the favorable interaction between its poly (ethylene oxide) chains with CO₂ molecules and inorganic fillers. However, the separation performance for CO₂/CH₄ mixture is still suffered from the moderate gas permeability and selectivity. To overcome this problem, in this work, amino-functionalized zeolite imidazolate framework (ZIF-7-NH₂) nanocrystals were used as fillers to blend with Pebax 1657 for fabricating mixed-matrix membranes (MMMs). XRD, Brunauer–Emmett–Teller (BET), scanning electron microscope, and ¹H nuclear magnetic resonance characterization indicated that ZIF-7-NH₂ with the highest crystallinity was synthesized. Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and Young's modulus showed that it has good interfacial interaction. Gas separation test results showed that both the CO₂ permeability and CO₂/CH₄ selectivity of the 31 wt% ZIF-7-NH₂/Pebax MMMs increased by 80 and 170%, respectively. The improved performance is attributed to the addition of ZIF-7-NH₂ nanocrystals and the favorable interfacial interactions between the polymer and ZIF-7-NH₂ nanocrystals. Furthermore, the polyvinylidene fluoride supported hollow fiber composite membranes also exhibit the long-term stability for CO₂/CH₄ separation.     

Effect of the ZIF‐8 Distribution in Mixed‐Matrix Membranes Based on Matrimid® 5218‐PEG on CO2 Separation

In theory, the combination of inorganic materials and polymers may provide a synergistic performance for mixed‐matrix membranes (MMMs); however, the filler dispersion into the MMMs is a crucial technical parameter for obtaining compelling MMMs. The effect of the filler distribution on the gas separation performance of the MMMs based on Matrimid®‐PEG 200 and ZIF‐8 nanoparticles is demonstrated. The MMMs were prepared by two different membrane preparation procedures, namely, the traditional method and non‐dried metal‐organic framework (MOF) method. In CO₂/CH₄ binary mixtures, the MMMs were tested under fixed conditions and characterized by various methods. Finally, regardless of the MMM preparation procedure, the incorporation of 30 wt % ZIF‐8 nanoparticles allowed to increase the CO₂ permeability in MMMs. The ZIF‐8 dispersion influenced significantly the separation factor.     

Mechanochemically synthesized ZIF-8 nanoparticles blended into 6FDA-TrMPD membranes for C3H6/C3H8 separation

The mixed matrix membranes (MMMs) consisting zeolitic-imidazolate framework-8 (ZIF-8) nanoparticles in a polymer have been of considerable interest in separation applications. The fillers used are mostly synthesized using the solvothermal method. In this study, the ZIF-8 nanoparticles were synthesized using a solvent-less and salt-free mechanochemical method and were added to 6FDA-TrMPD polyimide to prepare MMMs. The single gas permeation of C₃H₆ and C₃H₈ through the MMMs was investigated. The C₃H₆ permeability and C₃H₆/C₃H₈ ideal selectivity of a 20 wt% mechano-synthesized ZIF-8/6FDA-TrMPD MMM were 70% and 32% higher than those of the neat polymer membrane at 0.1 MPa and 308 K, respectively. The C₃H₆/C₃H₈ separation performance of the mechano-synthesized ZIF-8 MMM was similar to that of the conventional solvothermal-synthesized ZIF-8 MMM. This separation performance was in good agreement with the Maxwell model. Temperature and pressure dependence analyses confirmed that the mechano-synthesized ZIF-8 nanoparticles acted as molecular sieves in the MMMs for the C₃H₆ and C₃H₈ permeation.     

Study of morphology and gas separation properties of polysulfone/titanium dioxide mixed matrix membranes

Polysulfone (PSf)‐based mixed matrix membranes (MMMs) with the incorporation of titanium dioxide (TiO₂) nanoparticles were prepared. Distribution and agglomeration of TiO₂ in polymer matrix and also surface of membranes were observed by scanning electron microscopy, transmission electron microscopy, and energy dispersive X‐ray. Variation in surface roughness of MMMs with different TiO₂ loadings was analyzed by atomic force microscopy. Physical properties of membranes before and after cross‐linking were identified through thermal gravimetric analysis. At low TiO₂ loadings (≤3 wt%), both CO₂ and CH₄ permeabilities decreased and consequently gas selectivity improved and reached to 36.5 at 3 bar pressure. Interestingly, PSf/TiO₂ 3 wt% membrane did not allow to CH₄ molecules to pass through the membrane and this sample just had CO₂ permeability at 1 bar pressure. Gas permeability increased considerably at high filler contents (≥5 wt%) and CO₂ permeance reached to 37.7 GPU for PSf/TiO₂ 7 wt% at 7 bar pressure. It was detected that, critical nanoparticle aggregation has occurred at higher filler loadings (≥5 wt%), which contributed to formation of macrovoids and defects in MMMs. Accordingly, MMMs with higher gas permeance and lower gas selectivity were prepared in higher TiO₂ contents (≥5 wt%). POLYM. ENG. SCI., 55:367–374, 2015. © 2014 Society of Plastics Engineers     

Gas transport and mechanical properties of PDMS-TFS/LDPE nanocomposite membranes

This study investigates the effect of trimethylsiloxy fumed silica (TFS) on the mechanical and gas permeation properties of polymer nano-composite membranes. The membranes were produced by coating TFS incorporated polydimethylsiloxane (PDMS) at different loadings (5, 10 and 15 wt.%) on a porous low density polyethylene (LDPE) substrate which was formed by a melt-extrusion/salt leaching technique. The PDMS-TFS/LDPE membranes were characterized by SEM, TGA and DMTA. The results showed that good affinity between the PDMS treated TFS particles and PDMS matrix was obtained leading to improved mechanical and thermal properties. For gas permeation, CH₄ and C₃H₈ at different upstream pressure (50 to 80 psig) and temperature (27 to 55 °C) were investigated. The results showed that the C₃H₈/CH₄ ideal selectivity (17.6) and C₃H₈ permeability (1.89?×?10⁴ Barrer) through 10 wt.% TFS loaded membranes (PDMS-TFS10%/LDPE) were 41 and 14% higher than the neat membranes (PDMS-TFS0%/LDPE), respectively. The permeation results also indicate that the performance stability under the conditions investigated makes PDMS-TFS/LDPE membranes interesting for industrial applications.     

Facilitated propylene transport in mixed matrix membranes containing ZIF-8@Agmim core-shell hybrid material

The ZIF-8@Agmim core-shell hybrid material was synthesized via a favorable post-modification method of ion exchange (PMIE). This infrequent ZIF-8@Agmim core-shell structure maintains a well-integrated pore size that is almost the same as ZIF-8. The similar equilibrium isotherms with ZIF-8 and better kinetic separation toward propylene/propane than ZIF-8 render ZIF-8@Agmim to be an interesting candidate for propylene/propane separation. The core-shell hybrid nanomaterial was further used as nanofillers in the polymer of intrinsic microporosity matrix (PIM-1) for propylene/propane separation. The resultant mixed-matrix membranes (MMMs) exhibited a simultaneous increase in C₃H₆ permeability and C₃H₆/C₃H₈ ideal selectivity compared to pure polymer membrane owing to a synergistic effect of molecular sieving from ZIF-8 and π-complexation of Ag⁺ with propylene. The separation performance of the prepared MMM surpasses the upper bound line of polymer membranes. Furthermore, the hybrid materials possess superb photochemical stability and the corresponding MMMs exhibit excellent anti-aging property and long-term stability.     

Enhanced permeation performance of polyether-polyamide block copolymer membranes through incorporating ZIF-8 nanocrystals

Membrane-based CO2 separation is a promising alternative in terms of energy and environmental issues to other conventional techniques.Polyether-polyamide block copolymer (Pebax) membranes are promising for CO2 separation because of their excellent selectivity,but limited by their moderate gas permeability.In this study,fresh-prepared zeolitic imidazolate framework-8 (ZIF-8) nanocrystals were integrated into the Pebax(R)1657 matrices to form mixed matrix membranes.The resulting membrane exhibits significantly improved CO2 permeability (as high as 300％ increase),without the sacrifice of the selectivity,to the pristine polymer membrane.Several physical characterization techniques were employed to confirm the good interfacial interaction between ZIF-8 fillers and Pebax matrices.The effect of added ZIF-8 fillers on the transport mechanism through MMMs is also explored.Mixed-gas permeation for both CO2/N2 and CO2/CH4 was also evaluated.The separation performance for CO2/CH4 mixtures on the ZIF-8/Pebax MMMs is very close to the Roberson upper bound,and thus is technologically attractive for purification of natural gas.