Preparation and characterization of CO2-selective Pebax/NaY mixed matrix membranes

CO₂-selective Pebax/NaY mixed matrix membranes (MMMs) were prepared by incorporating NaY zeolite into Pebax matrix. The morphology, chemical groups, thermal stability, and microstructure of the MMMs were investigated by scanning electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction, respectively. The effects of zeolite loading amount, permeation temperature and pressure on the CO₂/N₂ separation performance of the resultant membranes were studied. The as-prepared MMMs are much superior to the pristine Pebax membranes in terms of permeability and selectivity. The CO₂ permeability and CO₂/N₂ selectivity can respectively reach to 131.8 Barrer and 130.8 for MMMs made by the starting materials containing 40 wt % NaY. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48398.     

Investigation of the effect of functionalized carbon nanotube and graphene oxide in guar gum-based mixed matrix membrane for gas separation application

The present study deals with preparing mixed matrix membranes (MMMs), a new polysaccharide-based natural polymer used as a matrix with functionalized carbon nanotubes (FCNTs) and graphene oxide (GO) used as an inorganic filler. This work identified the effect of the inorganic fillers (FCNTs or GO) with naturally occurring polymer for gas separation. The incorporation of fillers improves the gas separation performance of MMMs. In GG/FCNTs MMMs, the selectivities of CO₂/N₂ and CO₂/H₂ were enhanced by 55.24% and 57.89%, respectively. Moreover, in GG/GO MMMs, the selectivities of CO₂/N₂ and CO₂/H₂ were improved by 99.50% and 50%, respectively. The membrane was characterized by scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). The SEM analysis of GG/GO MMMs reveals layered structure, and GG/FCNTs MMMs create passages to transport gases. The Universal testing machine (UTM) is used to analyze the mechanical properties of pristine and modified membranes.     

Pebax–polydopamine microsphere mixed‐matrix membranes for efficient CO2 separation

Novel facilitated‐transport mixed‐matrix membrane (MMM) were prepared through the incorporation of polydopamine (PDA) microspheres into a poly(amide‐b‐ethylene oxide) (Pebax MH 1657) matrix to separate CO₂–CH₄ gas mixtures. The Pebax–PDA microsphere MMMs were characterized by Fourier transform infrared spectroscopy, scanning electron microcopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The PDA microspheres acted as an adhesive filler and generated strong interfacial interactions with the polymer matrix; this generated a polymer chain rigidification region near the polymer–filler interface. Polymer chain rigidification usually results in a larger resistance to the transport of gas with a larger molecular diameter and a higher CO₂–CH₄ selectivity. In addition, the surface of PDA microspheres contained larger numbers of amine, imine, and catechol groups; these were beneficial to the improvement of the CO₂ separation performance. Compared with the pristine Pebax membrane, the MMM with a 5 wt % PDA microsphere loading displayed a higher gas permeability and selectivity; their CO₂ permeability and CO₂–CH₄ selectivity were increased by 61 and 60%, respectively, and surpassed the 2008 Robeson upper bound line. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44564.     

Effective gas separation through graphene oxide containing mixed matrix membranes

In the present study, graphene oxide (GO) was incorporated into poly(vinylidene fluoride) (PVDF) and chemically modified PVDF (M‐PVDF) to prepare mixed matrix membranes (MMMs) for gas separation application. Performed analyses proved appropriate dispersion of exfoliated GO sheets in polymer matrices and sufficient compatibility at the interfacial phases. M‐PVDF based MMMs were thermally and mechanically more stable relative to the PVDF‐based MMMs. The oxygen containing functional groups in M‐PVDF was probably the main reason for this more stability. PVDF/GO MMMs rendered low gas permeability and high selectivity. Both impermeable GO sheets and crystalline phases of PVDF were responsible for such behavior. On the other hand, interestingly gas permeability of M‐PVDF/GO MMMs was enhanced while no substantial decline was recorded in gas selectivity. For instance, He and CO₂ permeability was increased 12.46% and 25.89%, respectively, compared to the pure PVDF membrane. This behavior originated from functional groups of M‐PVDF and the interaction of these groups with GO sheets. Since GO often amplified gas barrier properties of polymers, such increscent would be appreciable. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46271.     

Pebax-based mixed matrix membranes loaded with graphene oxide/core shell ZIF-8@ZIF-67 nanocomposites improved CO2 permeability and selectivity

In order to facilitate CO₂ transport in Pebax-based membranes, graphene oxide (GO)/core shell ZIF-8@ZIF-67 nanocomposites were loaded in Pebax copolymer to improve CO₂ permeability and selectivity. The 0.5 wt% GO doped core shell ZIF-8@ZIF-67, which gave highest CO₂ adsorption capacity of 1.12 mmol/g, was used as nanocomposite. The incorporated GO/core shell ZIF enhanced CO₂ adsorption via unsaturated metal sites (Zn-O or Co-O), because O atoms in GO substituted for N atoms coordinated with Zn and Co single atoms in core shell ZIF-8@ZIF-67. Positron annihilation lifetime spectroscopy indicated that GO-templated core shell ZIF nanocomposites generated extra free volume and provided low-resistance channels to facilitate CO₂ transport. Fourier transform infrared spectroscopy analysis revealed that hydrogen bonds were generated between Pebax polymer chains and GO-templated core shell ZIF which improved swelling resistance and reduced interface defects. Therefore, Pebax-based MMMs loaded with 5 wt% GO/core shell ZIF-8@ZIF-67 exhibited optimum CO₂ permeability (173.2 barrers) and ideal selectivity of CO₂/N₂ (61.9) and CO₂/H₂ (11.6), which were 99.7%, 66.4%, and 20.8% higher than Pebax membranes and surpass Robeson 2008 upper bound. The tensile strength increased by 17.6% to 28.8 MPa and elongation at break increased by 7.61%–554.6% when pure Pebax membranes were incorporated with 2.5 wt% GO/core shell ZIF-8@ZIF-67.     

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.     

Gas‐permeation performance of metal organic framework/polyimide mixed‐matrix membranes and additional explanation from the particle size angle

With MOFs of Cu₃(BTC)₂ and ZIF‐8 as the dispersed phases and four polyimides with CO₂ permeabilities ranging from 1.36 to 564 barrer as the continuous phase, the influence of metal organic frameworks on the gas‐separation properties of mixed‐matrix membranes (MMMs) was investigated. The results show that the gas permeabilities of all of the prepared MMMs greatly increased and even largely exceeded the predicted value of the Bruggeman model; for example, with the same Cu₃(BTC)₂ loading of 21.3 vol %, the O₂ permeability increase rate of our prepared Cu₃(BTC)₂/Matrimide 5218‐20 MMMs was 2.26 times, whereas that predicted by the Bruggeman model was only 1.05 times. In addition, when the gas permeability of the polymeric phase was far lower than the dispersed phase of ZIF‐8 or Cu₃(BTC)₂ compared with ZIF‐8, which had a particle size (R) around 150 nm, Cu₃(BTC)₂ of 5–15 µm showed a little better enhancing effect on the gas‐permeation performance of the MMMs. In addition to the properties of the dispersed and continuous phases, we speculated that the ratio between R of the dispersed phase to the membrane thickness (L) played an important role for MMMs; the larger R/L was, the greater the gas permeability of the MMMs was. This speculation was initially evidenced by the ZIF‐8/ODPA/TMPDA‐20 MMMs with different Ls. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45728.     

Size effects of graphene oxide on mixed matrix membranes for CO2 separation

Graphene oxide (GO)‐polyether block amide (PEBA) mixed matrix membranes were fabricated and the effects of GO lateral size on membranes morphologies, microstructures, physicochemical properties, and gas separation performances were systematically investigated. By varying the GO lateral sizes (100–200 nm, 1–2 μm, and 5–10 μm), the polymer chains mobility, as well as the length of the gas channels could be effectively manipulated. Among the as‐prepared membranes, a GO‐PEBA mixed matrix membrane (GO‐M‐PEBA) containing 0.1 wt % medium‐lateral sized (1–2 μm) GO sheets showed the highest CO₂ permeation performance (CO₂ permeability of 110 Barrer and CO₂/N₂ mixed gas selectivity of 80), which transcends the Robeson upper bound. Also, this GO‐PEBA mixed matrix membrane exhibited high stability during long‐term operation testing. Optimized by GO lateral size, the developed GO‐PEBA mixed matrix membrane shows promising potential for industrial implementation of efficient CO₂ capture. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2843–2852, 2016     

Preparation of poly(ether‐block‐amide)/poly(amide‐co‐poly(propylene glycol)) random copolymer blend membranes for CO2/N2 separation

A series of poly(amide‐co‐poly(propylene glycol)) (PA‐PPG) random copolymers with different content of PPG were designed by polycondensation reaction. These random copolymers were blended up to 60% with commercially available Pebax 2533. The blend membranes were characterized by Fourier‐transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), scanning electron microscope (SEM). Gas permeation properties of these blend membranes were investigated using five single‐gases (CO₂, H₂, O₂, CH₄, and N₂) at different temperature of 25–55°C and 1.0 atm. The impacts of content of PA‐PPG with different PPG content and operating temperature on CO₂ separation properties of Pebax/PA‐PPG blend membranes were studied. The results showed that CO₂ permeability gradually increased with the increasing operating temperature, whereas CO₂ permeability gradually decreased with the increase in content of PA‐PPG. CO₂/N₂ selectivity gradually increased with the increase in content of PA‐PPG. In particular, Pebax/PA‐PPG (50)–60% displayed excellent CO₂ and O₂ separation properties (P_CO2 = 79.7 Barrer and P_O2 = 13.6 Barrer, CO₂/N₂ = 34.7 and O₂/N₂ = 5.9) at 25°C and 1.0 atm. POLYM. ENG. SCI., 59:E14–E23, 2019. © 2018 Society of Plastics Engineers     

Effect of gas permeation temperature and annealing procedure on the performance of binary and ternary mixed matrix membranes of polyethersulfone,SAPO‐34, and 2‐hydroxy 5‐methyl aniline

This study investigated the effect of annealing time and temperature on gas separation performance of mixed matrix membranes (MMMs) prepared from polyethersulfone (PES), SAPO‐34, and 2‐hydroxy 5‐methyl aniline (HMA). A postannealing period at 120°C for a week extensively increased the reproducibility and stability of MMMs, but for pure PES membranes no post‐annealing was necessary for stable and reproducible performance. The effect of operation temperature was also investigated. The permeabilities of H₂, CO₂, and CH₄ increased with increasing permeation temperature from 35°C to 120°C, yet CO₂/CH₄ and H₂/CH₄ selectivities decreased. PES/SAPO‐34/HMA ternary and PES/SAPO‐34 binary MMMs exhibited the highest ideal selectivity and permeability values at all temperatures, respectively. For H₂/CO₂ pair, when temperature increased from 35°C to 120°C, selectivity increased from 3.2 to 4.6 and H₂ permeability increased from 8 to 26.5 Barrer for ternary MMM, demonstrating the advantage of using this membrane at high temperatures. The activation energies were in the order of CH₄ > H₂ > CO₂ for all membranes. PES/SAPO‐34/HMA membrane had activation energies higher than that of PES/SAPO‐34 membrane, suggesting that HMA acts as a compatibilizer between the two phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40679.     

Study the effects of Cloisite15A nanoclay incorporation on the morphology and gas permeation properties of Pebax2533 polymer

In this study, mixed matrix membranes (MMMs) were prepared using commercially available poly(ether‐b‐amide) (Pebax2533) as polymer matrix and organically modified montmorillonite (OMMt) as filler with the aim of investigating their gas permeation properties. The prepared membranes were characterized by Fourier‐transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), scanning electron microscope (SEM), thermal gravimetric analysis, and tensile strength analyses. Gas permeation properties of all the prepared membranes were evaluated at different pressures and clay loadings. Results of FTIR and SEM confirmed the appropriate adhesion between polymer and nanoclays so that no void formation was observed in the polymer/clay interface. XRD results showed that in low loading, clay dispersion occurred as exfoliated‐intercalated and at high loading as intercalated‐phase separated. Results of gas permeation test showed that by adding layered and impermeable clay particles to the polymer matrix, the permeation of soluble CO₂ gas reduced by 28% for the highest clay loading. By increasing of pressure from 2 to 6 bar, CO₂/CH₄ permselectivity increased at all nanoclay loadings. The highest CO₂/CH₄ selectivity was obtained for 6 wt % clay MMM at all pressures, while the highest CO₂/H₂ selectivity was achieved for neat polymer at 6 bar. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45302.     

Prestructured MXene fillers with uniform channels to enhance CO2 selective permeation in mixed matrix membranes

The packing pattern of two-dimensional (2D) sheet-like fillers in membranes is relatively random, leading to the unfavorable permeability from tortuous diffusion pathway. A new strategy that using prestructured materials with uniform channels as fillers was proposed. In this work, Ti₃AlC₂ is etched to prepare multilayered MXene (m-MXene), the channels aggregate as a whole unit, ensure the impossibility of ineffective packing compared with traditional individual sheets, largely facilitating the selective permeation. Then, the m-MXene/Poly (amide-6-b-ethylene oxide) (Pebax) MMMs are synthesized. SEM images demonstrate the accordion shaped structure of filler, which is the multi-channels laminates. Furthermore, the results of gas permeation test exhibit enhanced performance of m-MXene/Pebax MMMs. MMM with 0.5 wt.% m-MXene behaved best, CO₂ permeability of 86.22 Barrer as well as CO₂/N₂ selectivity of 104.85, transcending the Robeson upper bound (2008). Having distinct enhancement for CO₂ separation, the m-MXene/Pebax MMMs in this work offer prospective practical applications.     

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     

Effects of halloysite nanotubes on the morphology and CO2/CH4 separation performance of Pebax/polyetherimide thin-film composite membranes

Enhancing the performance of gas separation membranes is one of the major concerns of membrane researchers. Thus, in this study, poly(ether-block-amide) (Pebax)/polyetherimide (PEI) thin-film composite membranes were prepared and their CO₂/CH₄ gas separation performance was investigated by means of pure and mixed gases permeation tests. To improve the properties of these membranes, halloysite nanotubes (HNT) were added to Pebax layer at different loadings of 0.5, 1, 2, and 5 wt % to form Pebax-HNT/PEI membranes. Scanning electron microscopy, gas sorption, X-ray diffraction, Fourier-transform infrared, and differential scanning calorimetry tests were also performed to investigate the impact of HNT on structure and properties of prepared membranes. Results showed that both CO₂/CH₄ selectivity and CO₂ permeance increased by adding HNT to Pebax layer up to 2 wt %. By increasing HNT loading to 5 wt %, the CO₂/CH₄ selectivity decreased from 32 to 18, while CO₂ permeance increased from 3.25 to 4.2 GPU. Pebax/PEI and Pebax-HNT/PEI membranes containing 2 wt % of HNT were tested using CO₂/CH₄ gas mixtures at different feed CO₂ concentrations and feed pressure of 4 bar. The results showed that with increasing CO₂ concentration from 20 to 80 vol %, CO₂/CH₄ selectivity of Pebax/PEI composite membranes increased by 19%, while, in Pebax-HNT/PEI membrane, CO₂/CH₄ selectivity decreased by 40%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48860.     

CO2‐facilitated transport through poly(N‐vinyl‐γ‐sodium aminobutyrate‐co‐sodium acrylate)/polysulfone composite membranes

Poly(N‐vinyl‐γ‐sodium aminobutyrate‐co‐sodium acrylate) (VSA–SA)/polysulfone (PS) composite membranes were prepared for the separation of CO₂. VSA–SA contained secondary amines and carboxylate ions that could act as carriers for CO₂. At 20°C and 1.06 atm of feed pressure, a VSA–SA/PS composite membrane displayed a pure CO₂ permeation rate of 6.12 × 10^?6 cm³(STP)/cm² s cmHg and a CO₂/CH₄ ideal selectivity of 524.5. In experiments with a mixed gas of 50 vol % CO₂ and 50 vol % CH₄, at 20°C and 1.04 atm of feed pressure, the CO₂ permeation rate was 9.2 × 10^?6 cm³ (STP)/cm² s cmHg, and the selectivity of CO₂/CH₄ was 46.8. Crosslinkages with metal ions were effective for increasing the selectivity. Both the selectivity of CO₂ over CH₄ and the CO₂ permeation rate had a maximum against the carrier concentration. The high CO₂ permeation rate originated from the facilitated transport mechanism, which was confirmed by Fourier transform infrared with attenuated total reflectance techniques. The performance of the membranes prepared in this work had good stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 275–282, 2006     

Various Techniques for Preparation of Thin‐Film Composite Mixed‐Matrix Membranes for CO2 Separation

The application of thin‐film composite mixed‐matrix membranes (TFC‐MMMs) for gas separation is widely considered as an efficient separation technology. The principal methods for the preparation of TFC‐MMMs are dip‐coating, phase inversion, and interfacial polymerization comprising different types of support layers. These methods influence the CO₂ permeation over the selective and support layers. A comprehensive review is provided for capturing new details of progress achieved in developing TFC‐MMMs with detailed performance of gas separation in the previous few years. Various preparation techniques of TFC‐MMMs and their effect on the gas separation performance of the prepared membranes are described.     

The effect of ZIF-90 particle in Pebax/Psf composite membrane on the transport properties of CO2, CH4 and N2 gases by Molecular Dynamics Simulation method

Nowadays, mixed matrix membranes (MMMs) have considered by many researchers to overcome the problems of polymeric membranes. In addition, molecular dynamics (MD) and Monte Carlo (MC) simulation Methods are suitable tools for studying transport properties and morphology in MMMs. For this purpose, in this study using material studio 2017 (MS) software, the transport properties of CO₂, CH₄ and N₂ in Pebax, Psf neat Pebax/Psf composite and Pebax/Psf composite filled with ZIF-90 particles have been investigated. By adding Psf to Pebax matrix, the selectivity of CO₂/CH₄ and CO₂/N₂ gases has significantly increased. In addition, adding ZIF-90 particles to the Pebax/Psf composite increased the permeability of CO₂, CH₄ and N₂ compared to neat and composite membranes. The morphological properties of the membranes, such as the fractional free volume (FFV), radial distribution function (RDF), glass transition temperature (T_G), X-ray diffraction (XRD) and equilibrium density have calculated and acceptable results have obtained.     

Modeling of hydrogen separation through porous YSZ hollow fiber‐supported graphene oxide membrane

In this work, hydrogen (H₂) permeation fluxes through 230 nm‐thick graphene oxide (GO) membrane deposited on porous YSZ hollow fiber were measured and correlated to an explicit H₂ permeation model. H₂ fluxes through such GO‐YSZ hollow fiber membrane increased from 4.83 × 10^?8 mol cm^?2 s^?1 to 2.11 × 10^?7 mol cm^?2 s^?1 with temperature rise from 20 to 100 °C. The activation energy of H₂ permeation was determined by the linear regression of the experimental data and was applied in the theoretical calculations. The model predictions fit well the temperature dependent and the argon sweep gas flow rate dependent H₂ fluxes data. Using the derived permeation model, the effects of vacuum pressure at lumen side and H₂ partial pressure at shell side, membrane area, and GO membrane film thickness on the membrane performance were simulated and discussed to provide insights for practical applications. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2711–2720, 2018     

Highly efficient recovery of propane by mixed‐matrix membrane via embedding functionalized graphene oxide nanosheets into polydimethylsiloxane

To construct rapid C₃H₈ transport pathways in polymer matrix, alkyl chain‐functionalized graphene oxide (GO) was prepared via grafting octadecylamine (ODA) molecules and then embedded into polydimethylsiloxane (PDMS) matrix to obtain high‐efficiency mixed matrix membranes (MMMs). The incorporation of alkyl chains contributes to lowering the surface energy of GO nanosheets and providing higher affinity with PDMS matrix. Additionally, the alkyl chains on the surface of ODA‐functionalized GO nanosheets (ODA‐GO) are in favor of C₃H₈ adsorption, thus conferring continuous and specific transport pathways for C₃H₈. The optimized membrane with ODA‐GO loading of 0.3 wt% exhibits the C₃H₈ permeance of 1897 GPU and the C₃H₈/N₂ ideal selectivity of 67, which are 50.2 and 72.5% higher than those of bare PDMS membrane, respectively. The simultaneous enhancement of C₃H₈ permeance and C₃H₈/N₂ ideal selectivity indicates that ODA‐GO is an effective filler applied in MMMs for C₃H₈ recovery. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3501–3510, 2017     

The Influence of Cu3(BTC)2 metal organic framework on the permeability and perm‐selectivity of PLLA‐MOF mixed matrix membranes

Poly(l ‐lactic acid) (PLLA) ‐ 20% (w/w) and Cu₃(BTC)₂ metal organic framework (MOF) based mixed matrix membranes (MMMs) were fabricated by a vertical corotating twin screw microcompounder followed by an injection molding process. Water vapor, CO_2, O₂, and selected aroma mass transfer properties of PLLA and PLLA MMMs were evaluated. The CO₂/O₂ perm‐selectivity of PLLA (α_CO2/O2) MMMs increased from 7.6 to 10.3 with the incorporation of 20% Cu₃(BTC)₂ MOF. Gravimetric permeability studies of trans‐2‐hexenal performed at 23°C and 50% RH indicated that permeability coefficient of PLLA MMMs increased by around 60% as compared to regular PLLA film. However, no changes in mass transfer rates were observed for acetaldehyde. Furthermore, the thermal processing parameters as well as the presence of MOF did not show any significant effect on the molecular weight of the PLLA matrix nor on the crystalline structure of the Cu₃(BTC)₂ MOF, which was confirmed by both gel permeation chromatography and X‐ray diffraction studies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42764.