A stable polymeric chain configuration producing high performance PEBAX-1657 membranes for CO2 separation

Although PEBAX-1657 is one of the promising polymeric materials for selective CO2 separation, there remain many questions about the optimal polymeric structure and possibility of improving performance without adulterating its basic structure by impregnating inorganic fillers. In order to improve the gas separation performance, low thickness PEBAX membranes were synthesized under steady solvent evaporation conditions by keeping in mind that one of its segments (nylon 6) shows structural variance and molecular orientation with a change in the evaporation rate. Furthermore, phase pure zeolite nanocrystals with cubic (zeolite A) and octahedral (zeolite Y) shapes have been synthesized through liquid phase routes using microwave hydrothermal reactors. The average sizes of zeolite A and Y crystals are around 55 and 40 nm, respectively. The inspection of XRD, DSC and Raman shift of PEBAX membranes demonstrates the formation of a stable polymeric structure with an improved crystalline state which results in high CO2 permeability membranes. The CO2 permeability as well as diffusivity increase with a decrease in membrane thickness and reach a maximum value of 184.7 Barrer and 2.6 × 10−6 cm2 s−1, respectively. The as-fabricated pristine PEBAX membrane shows much better performance in terms of permeance (CO2 184.7 Barrer), diffusivity (CO2 2.6 × 10−6 cm2 s−1) and selectivity (CO2/N2 59.7), which substantiate its promising prospects for CO2 capture. This exceptional performance of the pristine PEBAX membrane arises from the free volume generated during the steady polymerization. This reported approach for PEBAX membrane synthesis provides a direction in the design of membrane fabrication processes for economic CO2 separation.


Introduction
Global warming is mainly caused by the emission of greenhouse gases and 72% of the total emitted greenhouse gases are carbon dioxide (CO 2 ), 18% methane and 9% nitrous oxide (NO x ).Therefore, CO 2 emission is the primary cause of global warming, and human activities are mainly responsible for greenhouse gas emission into the earth environment. 1Thus, CO 2 capture, separation, and storage have been considered as one of the most important technological efforts to combat the global warming challenge.][4][5][6][7][8][9][10] Particularly, the amine scrubbing based post-combustion CO 2 capture process has large human health and environmental concern because of solvent emissions during the processing.Furthermore, a high amount of energy is needed for CO 2 desorption which results in efficiency loss in the case of amine-based scrubbing.
Inorganic and polymeric membranes are two major players for CO 2 capture. 11Although, inorganic membranes have also been extensively investigated for gas separation due to their exceptional separation performance and incredible thermal and chemical stability, their cost and lack of processability are the major issues for their large-scale production.Furthermore, assembling of inorganic membranes into high packing density membrane modules is critical for the ue gas process.On the other hand, polymeric membranes have emerged as an ideal candidate for large scale processing plants. 12,13However, polymer-based membranes have a major drawback, the socalled permeability-selectivity trade-off, i.e., either increase in permeability or decrease in selectivity or vice versa. 145][26][27][28][29][30][31][32][33][34][35][36][37][38] PEBAX consists of two monomers polyethylene oxide (PEO) and polyamide (PA), where the earlier component provides exibility and high CO 2 permeability due to its high affinity with the polar CO 2 molecule, while the latter component imparts mechanical strength to the membrane.As ether oxygen moieties have a signicant affinity to acid gases, PEBAX is considered as one of the best candidates for CO 2 separation from light gases. 24,32The perfect balance between permeability and CO 2 selectivity can be achieved by increasing the free ow of gas molecules through the polymeric membrane without altering the surface structure of the polymer.
Polymer free-volume, the fraction of the volume not occupied by the electronic clouds of the polymer, plays an important role in the transport properties of low molecular weight species and gases.5][46][47] Not only the overall amount of free-volume but also the distribution of the effective micropore size is likely to have a signicant inuence on polymer properties if the free-volume elements are interconnected.The use of inorganic llers in mixed matrix membrane (MMM) is to inuence the free volume. 15,24,40However, the addition of cost-ineffective nano-size inorganic llers generally shows negative effects on the selectivity with little improvement in permeability.If the addition of nano-inorganic llers is just to improve the permeability of the membrane, then it is better to nd an alternative method to achieve the same.][50][51][52][53] In this reported paper, attempts have been made to improve the permeability as well as CO 2 selectivity of the PEBAX-1657 membrane by improving the polymeric structure and controlling the free volume of the membrane.This work reects that the free volume of the PEBAX-1657 membrane can easily be controlled by controlling the polymer chain conformation.Furthermore, to ascertain the structural as well as chemical reforms in the as-fabricated pristine PEBAX membrane elaborate diffraction, electron scanning, thermal, spectroscopic, etc., analyses were conducted.Moreover, a number of experiments were performed to compare the selectivity of pristine PEBAX-1657 membranes with that of nano-molecular sieves (Scheme 1) embedded mixed matrix membranes (MMMs).

Zeolite molecular sieve synthesis
Zeolite molecular sieves (zeolite A (LTA type) and zeolite Y (FAU type)) having different porous characters (structure and size) and Si/Al ratios have been synthesized through liquid phase routes using a microwave hydrothermal reactor (CEM, Discover-909150, maximum power of 300 W).Detailed synthesis conditions with chemical compositions and their structural properties have been summarized in Table 1.Aer the synthesis, the resultant milky suspensions containing nano-size zeolite molecular sieves were cooled to room temperature and diluted with deionized water.The resulting nano-crystals were then separated from the mother liquor by high speed centrifugation at 20 000 rpm for 20 min at 4 C followed by repeated redispersion in deionized water and centrifugation (washing step was repeated 5 times).To avoid the aggregation or coagulation of the nano-particles during drying, the nally collected wet zeolite particles were directly dispersed in DIW.The reported percentage of zeolite molecular sieves loaded on PEBAX-1657 membranes was directly obtained from the wet sample.

Membrane synthesis
Fig. S1, ESI † presents the stepwise preparation procedure for the pristine PEBAX and double layer PEBAX/nano-molecular sieve MMMs.PEBAX® 1657 pellets were dissolved in EtOH : H 2 O (70 : 30 wt%) solvent at 80 C for 2 h with high speed stirring in a microwave hydrothermal reactor to obtain 2.5% PEBAX solution.Different thickness membrane lms were obtained by pouring different amounts of polymer solution into a Teon Petri dish (f 85 mm).Subsequently, the polymer solution containing Teon Petri dish was covered with lter papers (F1113 grade, Chmlab) to slow down the evaporation of solvent allowing the formation of a polymeric membrane with uniform thickness and better crystallinity.The polymeric solution was dried for 2 days at 40 C. Once dried, the lm was placed under vacuum for 24 h for complete solvent removal from the lm.Aer this period, the lm was allowed to cool to room temperature under vacuum.A 50 mm diameter circular sample was cut from the lm and used for permeation tests, whereas, the PEBAX/nano-molecular sieve MMMs were fabricated by just casting the inorganic ller suspension in 1% PEBAX solution (EtOH : H 2 O: 70 : 30) on a dried PEBAX lm as shown in Fig. S1, ESI † followed by drying.Casting of inorganic molecular sieves on the polymeric lm instead of mixing with polymer solution was performed to avoid the void formation between the high concentration polymer and inorganic particles at their interface.The resultant membranes were denoted as P 75 , P 40 , P 22 , P 14 , P 63A , and P 56Y , where digits in the subscript represent the thickness of the membrane and letters molecular sieves.

Zeolite particles and membrane characterization
Powder X-ray diffraction studies of the nano-molecular sieves and PEBAX membranes were performed on a PANalytical: X'Pert PRO diffractometer with Cu-Ka radiation (l ¼ 1.5418 Å) and the data were collected in the 2q range of 5-60 with a step size of 0.02 s À1 .Phase identication for zeolites A and Y was performed with the help of JCPDS les for inorganic compounds (LTA #97-002-4901 and FAU # 98-003-4277).The morphological characteristics, particle size, and membrane thickness were evaluated with a scanning electron microscope (SEM, JEOL-JSM-7000F).The membrane samples were prepared by fracturing the membrane in liquid nitrogen and subsequent sputter coating of palladium.The average particle size and particle size distributions of the inorganic llers were measured by light scattering analysis (Nanotrac Wave, Microtrac, Inc.) at 298 K. Transmission electron microscopy (TEM) images were obtained using an FEI Tecnai™ G 2 F30 electron microscope, operating at 300 kV.The particle size distribution (PSD) in volume percent was calculated by using Microtrac FLEX 11 operating soware.The thermal properties and glass transition temperatures (T g ) of Detailed reaction conditions for the as-synthesized zeolite nano-molecular sieves and their structural properties pristine PEBAX membranes were determined using a differential scanning calorimeter (DSC) (TGA/DSC 1 STAR e system METTLER TOLEDO instruments).The measurements were carried out using a standard heating-cooling-heating procedure at a rate of 10 K min À1 in a nitrogen atmosphere.Furthermore, the chemical structure of the as-fabricated PEBAX membranes was characterized by using Raman spectra, which were recorded by using a LabRAM HR Evolution 800, Raman Spectrometer from Horiba Scientic (785 nm diode laser excitation).Fourier transform infrared spectroscopy (FTIR, ALPHA-Platinum ATR, Bruker) spectra of pristine PEBAX membrane samples were recorded in the range of 600-3600 cm À1 with a resolution of 1.4 cm À1 (64 scans) to assert the changes in the polymeric chain conformation.Water vapor adsorption/ desorption experiments were performed at 298 K using an automatic adsorption measurement apparatus, BELSORP-max (BEL Japan, Inc.), and each sample was outgassed for 6 h at 423 K before analysis.A $66 point water vapor adsorption/ desorption isotherm has been recorded and used for surface area and total pore volume calculation.The experimental values of membrane density were determined at 25 C using Archimedes' principle with an electronic balance (Mettler Toledo XS205) equipped with a density measurement kit.An auxiliary liquid, silicon oil (r o ¼ 0.913 g cm À3 ), with known densities was used to evaluate the density, and to affirm the variation in fraction free volume (FFV).A piece (approximately 4 cm 2 ) of each polymeric membrane was introduced into a sample pan and basket for weight measurement in air and the liquid phase, respectively.Considering some degree of hydrophilicity of the PEBAX membrane, two different uid (de-ionized water and silicon oil) were selected to minimize the source of error due to the liquid-polymer interaction over the time scale of equilibration during weight measurement.The experimental values of density (r p ) were calculated by using the following equation: where W air and W liquid are the membrane weight in air and in the liquid phase, respectively.The fraction free volume (FFV) and specic free volume (SFV) of pristine PEBAX membranes were calculated using the following equations based on the density data: 24 where r p is the density of PEBAX, and n w is the van der Waal's volume (0.590 cm 3 g À1 ) of the repeat unit of PEBAX. 24

Gas permeation measurement
The permeability of the polymeric membranes and MMMs were measured at room temperature (25 C) and at a feed pressure of 2.7 bar using a single gas with a xed-volume pressure increase instrument. 54The permeability was measured directly and the time lag method was applied to the recorded data to determine the diffusivity coefficient.The solubility coefficient was taken as the ratio of the permeability to the diffusivity coefficient.The schematic diagram of the permeation system is shown in Fig. 1.
A at sheet circular cell affixed with a mesh to support the membrane of effective area 15.2 cm 2 was placed in a thermostat oven to control the temperature.Before analysis, the membranes were evacuated for at least 24 h to remove the previously adsorbed species.Moreover, to achieve accurate temperature apart from the gas cylinder, all other equipment/ pipelines were installed inside a thermostat oven as shown in Fig. 1.Gas transport in dense polymer membranes can be described by the solution-diffusion mechanism, in which the gas penetrants are absorbed into the membrane from the upstream feed and then diffuse through the membrane to the downstream permeate. 28,36Permeability (P) is an intrinsic property of the membrane material, which can be written as the product of diffusivity (D) and solubility coefficient (S): where P i , D i , and S i represent the permeability (Barrer), diffusivity (cm 2 s À1 ), and solubility (cm 3 (STP) cm À2 cmHg À1 ) coefficients of the penetrant component i, respectively.
In the ideal case of mass transport, P, D, and S are independent of feed/permeate pressure.Therefore, the selectivity of a polymer membrane for gas A over gas B will be the ratio of the gas permeability coefficients: On using eqn ( 4) and ( 5) becomes; where D A /D B and S A /S B are the diffusivity and solubility selectivity, respectively.). 55,56The water vapor adsorption on both of the zeolite molecular sieves (Fig. S6, ESI †) displays a characteristic Type I shape in the IUPAC classication.These adsorption isotherms also highlight their greater water adsorption affinity as these microporous zeolite molecular sieves capture water vapor at a very low P/P o value with steep uptake behavior.The experimentally calculated values of textural parameters of the zeolite molecular sieves reported in Table S1 (ESI †) reveal that zeolite Y has a higher surface area (1093.1 m 2 g À1 ) as well as total pore volume (0.35 cm 3 g À1 ) than zeolite A.

Membrane characterization
3.2.1 Morphology evaluation.The SEM analysis of pristine PEBAX and PEBAX/nano-molecular sieve MMMs has been performed to investigate the surface smoothness, distribution of zeolite particles in the PEBAX polymer matrix, interfacial adhesion of the polymer and inorganic ller, accurate measurement of membrane thickness, etc. Photographic camera images and surface SEM micrographs of the membranes are presented in Fig. S7 (ESI †), whereas crosssectional SEM micrographs and magnied surface and crosssectional views of the MMMs are reported in Fig. 3. Photographic and surface SEM images display the clean and uniform growth of the pristine PEBAX membranes as well as MMMs.In the case of MMMs, the homogeneous distribution of nanozeolite crystals of zeolites A and Y on the P 63A and P 56Y membrane surfaces can easily be observed.Moreover, these images also demonstrate the absence of nano-crystal agglomeration and interfacial void formation in the polymeric matrix.Furthermore, the cross-sectional SEM image of the membranes (Fig. 3) indicates that the uniform growth throughout the membrane thickness remains almost the same.The obtained membrane thickness value from the cross-sectional SEM images was used in the calculation of the gas permeation properties for each membrane.In addition, the cross-sectional images of P 63A and P 56Y membranes (Fig. 3) establish the successful growth of MMMs on the pristine PEBAX polymeric lm.A little variation in the thickness of P 63A (63 mm) and P 56Y (56 mm) MMMs may arise from the difference in inorganic ller crystal sizes as zeolites A and Y crystals were 55 and 40 nm in size, respectively.Two distinct layers of almost the same thickness can be seen in these images (Fig. 3).
The magnied view of the surface and cross section of PEBAX/nano-molecular sieve MMMs containing 5 wt% polymer (Fig. 3) evidences that nano-zeolite crystals were comprehensively distributed in the PEBAX matrix without any aggregation and interfacial zeolite-polymer voids.The polymer was adhered well to the nano-zeolite crystals due to the rubbery nature of the continuous polymer phase and the presence of so polymeric segments and smooth surfaced real nano-sized (around 50 nm) inorganic ller particles.The real nano-sized inorganic ller leads to the formation of a homogeneous and stable suspension in the polymeric solution as well as in the solvent which results in defect free MMMs.
3.2.2Crystallinity assessment.X-ray diffraction measurements were performed to evaluate the chain packing in the polymeric lms.Representative XRD patterns for the pristine PEBAX membranes and MMMs of different thicknesses are collectively reported in Fig. 4 to compare the variation in diffraction patterns or the crystalline state with the polymerization or packing of PEO-PA units.PEBAX is a block copolymer with exible polyether segments (polyethylene oxide) and a rigid block of polyamide (nylon 6); therefore XRD patterns reect the semi-crystalline nature of various thickness polymeric lms (Fig. 4 P 75 , P 40 , P 22 , and P 14 ). 57The strong peak (21.4 ) and a broad peak (at 24.0 ) attributed to the crystalline PA6 phase correspond to d-spacing values of 4.15 and 3.70 Å, respectively.The decrease in the thickness of the polymeric lm results in highly crystalline PA6 and PEO phases.Therefore, the sharp peak at a 2q value of 26.7 (d-spacing value 3.34 Å) is attributed to the PEO phase.In addition to the characteristic PEO phase peak (26.7 ), a low intensity peak for the same has also been observed at 29.5 in the XRD patterns of P 14 and P 22 pristine PEBAX samples.Moreover, the direction of arrows in Fig. 4 demonstrates the relative increase in peak intensities.On comparing the diffraction peaks corresponding to the PA6 phase we nd that the peak intensity ratio of 21.4 /24.0 peaks increases with a decrease in the thickness of the polymeric membrane.Furthermore, the peak intensity of the PEO phase also increased with a decrease in membrane thickness.Hence,  these diffraction patterns affirm that low thickness PEBAX membranes have better polymeric chain arrangement and crystallinity in comparison to thick membranes.It has been reported that nylon 6 (PA6) has two different crystalline structures, i.e., a, and g-forms.The molecules in the a crystal exhibit a fully extended, planar zigzag chain conrmation which is a thermodynamically stable structure and is well formed under slow crystallization while those in the g-form crystal form a helical, metastable structure favored by rapid crystallization. 58,59Thus, these shis in the diffraction peak intensity (Fig. 4) may be attributed to the chain packing in the copolymer lms.Moreover, it is possible that the drying duration (2 days at 40 C) is not sufficient for P 40 and P 75 membrane samples to dry completely under closed or controlled evaporation conditions.Therefore, understanding and controlling the crystal structures of polymers are pursued to gain insights into their mechanical properties and chain alignment.
To conrm the above ndings, a comparison of XRD results with literature reported studies has been performed.On comparing Fig. 4 and S8, ESI, † we found that the as-fabricated membranes have distinct peaks for PA6 and PEO crystalline phases whereas in earlier reported studies no such distinction has been made.Most of the diffraction patterns in Fig. S8, ESI † show a broad peak ranging from 15-25 with a shoulder or small intensity peak, which implies the irregular packing of the polymer chains.The XRD patterns also evidence the formation of a metastable, helical g-form type (PA6) structure in these PEBAX membranes.Moreover, these diffraction patterns (Fig. S8, ESI †) display a remarkably lower degree of crystallinity in comparison with P 14 , P 22 , P 40 , and P 75 membranes (Fig. 4).

Thermal analysis.
According to the TGA results (Fig. S9a, ESI †), the thermal weight loss proles for different thickness pristine PEBAX membranes follow the same trend and the pyrolysis of the membranes occurs between 350 and 450 C which is in accordance with earlier reports. 32,60,61This deterioration of polymeric membranes is mainly associated with the decomposition reaction of the polymer precursors.
Furthermore, to evaluate the thermal properties, polymeric chain rigidity, crystallization tendency, T g and T m (melting temperature) of polymers/segments, DSC analyses were performed.As reported in Fig. S9b (ESI †), the typical peaks of PEO and PA6 crystalline phases establish the semi-crystalline and phase separation characteristics of PEBAX membranes. 38In the case of the PEO segment, a small variation in the melting peak can be noticed.The area of the T m PEO peak decreases with an increase in the membrane thickness whereas an increase in melting temperature has been observed which depicts the change in the crystallinity of the PEO segment.Moreover, a decrease in T g values from À52.3 C to À54.0 with a decrease in membrane thickness indicates the polymeric chain mobility and much regular arrangement.Furthermore, the T g values reported in Fig. 5b for the PEO segment are much lower than previously reported values for pristine PEBAX membranes, where Xin et al., 35 Li et al., 38 Wang et al. 30 and Rahman et al. 1 reported À50.4 C, À51.6 C, À51.4 C, and À51.0 C for pristine PEBAX 1657 membranes, respectively.In addition to variation in the DSC prole of the PEO segment with a change in membrane thickness, a split in the T m peak of the PA segment for the P 75 membrane has also been observed which conrms the dual phase formation (a and g PA6) during P 75 membrane crystallization.Therefore, DSC observation affirms the XRD analysis ndings.
3.2.4Chemical structure analysis.Vibrational spectroscopy, which is sensitive to the molecular conrmation of polymers, also demonstrated similar ndings to those of XRD. 59,62As shown in Fig. 5, the spectrum of the high thickness P 75 membrane exhibits different peak positions and intensities of characteristic peaks than that of the thin P 14 membrane, which implies a change in the polymeric chain conguration.Additionally, there are obvious differences in the C-C stretching region (900-1150 cm À1 ) and the C-N-H bending region (1300-1350 and 1440-1490 cm À1 ), and in the intensity of the amide regions (Fig. 5).The amide band at 1632 cm À1 is primarily attributed to the CO stretch, while another amide mode is a combination of the C-N-H stretching and the C]O in-plane bending of the amide group (-C(O)-NHC-).The C-C stretching region is composed of four primary peaks, 1022, 1062, 1072 and 1127 cm À1 .The 1062 and 1127 cm À1 peaks are indicative of an all-trans C-C backbone conformation while the 1080 cm À1 peak is attributed to the presence of gauche bonds in the polymeric lm.The C-N-H bending region of the Raman spectrum is also sensitive to the conformation (planar or nonplanar) of the amide group.Bands observed in the regions of 1270-1350 and 1440-1490 cm À1 are indicative of different amide conformations.Furthermore, the disappearance or decrease in the intensity of the 1465 cm À1 peak in the spectrum of the P 14 membrane evidences the change in the conformation of the polymer.If we go by the explanation given by Giller et al. 59 and Stephens et al. 63 for PA6, then we can also expect more than one energetically favorable crystalline structure (and/or chain conformations) in PEBAX membranes.Furthermore, nylon 6 is an important constituent of the PEBAX polymer and it imparts strength to PEBAX membranes.The -NH(CH 2 ) 5 (CO)-repeating groups lead to a structure in which the peptide units (NH-CO) provide hydrogen bonding between polymer chains.Although nylon is crystalline, the presence of the crystalline lamella in an amorphous matrix makes it difficult to obtain precise crystallography. 64It has been well documented that nylon 6 exists in mainly two forms of regular crystal structures: a form (with amide bonds parallel to the methylene sheets) and g form (with amide bonds perpendicular to the methylene sheets), as shown in Fig. 6. 58,59,[64][65][66] Out of these two forms, the a form is considered to be more stable than the g form.If we go by these reported ndings for nylon 6, then we can expect that the asfabricated membranes have a different polymer conformation than that in earlier published reports.Thus, the polymeric chains in the crystalline zone of PEBAX may favor bonding among chains, and the nature of these folds affects the optimum chain spacing, chain structure/conguration, and connection between them.In simple words, the conformation of the PEBAX membrane has a high inuence on its single gas permeation performance.
FTIR spectroscopy was used to explore the polymer conformation and interfacial interaction between the polymeric chains in the as-fabricated high permeability PEBAX membranes.Fig. 7 shows the FTIR spectra of the different thickness PEBAX membranes.The inset image in each spectrum reveals that there is a considerable difference between the vibrational peaks of low thickness and high thickness membranes (Fig. 7).A close look at the inset image in Fig. 7 P 14 reveals a strong peak at 1461 cm À1 but with the increase in the thickness of the polymeric membrane in the P 44 membrane sample, a shoulder appears which further changes to a low intensity peak (1440 cm À1 ) in the P 75 sample.On the other hand, the 1275 cm À1 peak in P 14 and P 22 polymer lms disappeared in P 40 and P 75 membranes which indicates a change in the polymeric chain arrangement with an increase in the thickness of the membrane.In addition to the disappearance of the 1275 cm À1 peak in the P 75 membrane spectrum, a shi in  the peak position (to 1245 cm À1 ), broadening and appearance of weak shoulder peaks have also been noticed.Moreover, vibrational peak patterns, especially in the 1200-1500 cm À1 wave number region of the as-fabricated PEBAX membranes, are unquestionably different from the spectra reported by Murali et al., 26 Wang et al., 30 Xiang et al. 32 and Li et al. 38 The appearance and disappearance of vibrational peaks in the 1200-1500 cm À1 wave number region demonstrate transformation in the polymer chain conformation and interfacial interactions as highlighted in Fig. 7. 58,67 The interaction between the two different classes of crystal structures formulated with different polymeric chain packing schemes in nylon 6 can also be considered as a crucial factor for a stable polymeric chain conguration in PEBAX membranes.The FTIR spectrum of the P 75 membrane also shows some change in the intensities and position shi of the symmetric stretching vibration peak of the -CH 3 group highlighted by a dotted circle.Furthermore, the spectra reported in Fig. 7 reveal an unequivocally better polymeric chain arrangement and chemical structure than earlier reported spectra for pristine PEBAX 1657 membranes. 26,32The sharp and strong bands at 1732 and 1636 cm À1 represent C]O stretching vibration in the two types of amide groups, whereas 1541 cm À1 peaks correspond to N-H deformation of the PA6 segment. 38For the pristine PEBAX membrane, the characteristic peak at 1096 cm À1 is mainly attributed to the C-O stretching vibration of the PEO segment.As reported by Zheng and Xu, 67 Ruiz-Hitzky and Aranda, 68,69 and Papke et al., 70 the peaks at 949 and 848 cm À1 assigned to the CH 2 rocking vibration of methylene groups in a gauche conformation indicate the possible helical structure of the PEO segment in the PEBAX membrane.From the Raman and FTIR spectra discussion, we can conclude that the polymer chain conformation, hydrogen bonding and interaction between polymeric chains play decisive roles in the free space and polymeric membrane performance.
3.2.5 Free volume assessment.Free volume is useful for explaining the different aspects of polymers such as polymeric chain arrangements, mobility, and permeability but at the same time, it is relatively difficult to estimate with full accuracy.In the PEBAX membrane the PEO component mainly selectively interacts with polar gases such as CO 2 to have high solubility selectivity towards polar gases.Ideally, based on the solutiondiffusion model for dense membranes, the solubility selectivity due to the PEO segment should enhance the CO 2 permeability if the diffusivity component PA6 is arranged well and not adversely affected by the PEO segment. 18As XRD and DSC studies affirmed the regular arrangement of the polymeric chain and high crystallinity PEBAX membrane formation, it becomes essential to evaluate the FFV and SFV.The FFV and SFV of pristine PEBAX membranes were estimated based on the group contribution method coupled with density measurements and the results are listed in Table 2.As shown, the FFV values of PEBAX membranes increase with a decrease in the membrane thickness which is favorable for enhancing the permeability. 38The P 14 membrane of 14 mm thickness has the highest value of FFV as well as SFV.The obtained FFV values based on membrane density data are in good agreement with T g values and crystalline character, as obtained from DSC and XRD results.In these terms, it seems clear that the glass transition temperature and the fraction of free volume have a distinct correlation.Virtually in the case of rubbery polymers, the FFV increases with decreasing T g . 71These observations indicate that the planar polymeric chain conformation with a stable polymeric structure formed under slow crystallization generates inter-chain spacing which results in signicantly high FFV PEBAX membranes.The as-fabricated PEBAX membranes not only show a better polymeric structure but also have a high value of FFV in comparison to earlier reports. 16,383 Single gas permeation performance assessment 3.3.1 Gas permeability of pristine PEBAX membranes and MMMs.The single gas permeation performance of polymeric membranes and MMMs was measured by a single gas permeation test of CO 2 , N 2 , O 2 , and CH 4 .The polymeric membranes were different thickness PEBAX membranes whose thickness varies from 14-75 mm, and the MMMs were the polymeric membranes with 5 wt% zeolite nanoparticles (zeolites A and Y).The CO 2 , N 2 , O 2 , and CH 4 permeability and their intrinsic selectivity for PEBAX and MMMs have been presented in Table 3.The tabulated values of permeability and permselectivity demonstrate a distinct relationship between CO 2 permeability and the thickness of the membrane.It can be noticed that the high thickness PEBAX membrane (P 75 ) displays a low value of permeability while the thin P 14 membrane shows exceptionally high CO 2 permeability.As can be seen in Table 3, the decrease of membrane thickness increases the permeability of CO 2 while the permeability values of the other gases vary slightly.Consequentially, the ideal permeation selectivity values for CO 2 /N 2 , CO 2 /O 2 , and CO 2 /CH 4 were increased with decreasing membrane thickness and stable PEBAX lm formation.As there is a direct relationship between gas permeability and FFV, the increase of CO 2 permeability and selectivity over the other gases can be attributed to increases in FFV.The increased selectivity can also be attributed to change in chain stiffness with membrane thickness variation.Unfortunately, the loading of zeolites A and Y onto PEBAX membranes shows a negative effect on membrane selectivity.In the case of MMMs (P 56Y ), an increase in gas permeation was observed for all the gases which results in low CO 2 permselectivity.However, selectivity values are comparable with those of the pristine PEBAX P 75 membrane.
In order to obtain further insight into the role of the improved characteristics of the membrane in slow solvent evaporation and reduced thickness in gas permeation, the The CO 2 gas permeation performance of the as-fabricated pristine PEBAX membranes was compared.The CO 2 gas permeation performance of some representative pristine PEBAX, as well as PEBAX, based MMMs is compiled in Table S3 (ESI †) with detailed experimental conditions.Table S3 (ESI †) substantiates that the permeability as well as the selectivity of the as-fabricated pristine PEBAX membrane for CO 2 and N 2 separation is not only higher than that of literature reported pristine PEBAX membranes but also higher than that of MMMs.These results also show that we fabricated a high performance membrane without using any inorganic ller and with very low polymer concentration (2.5%).Furthermore, the thickness of the as-fabricated membrane (14 mm) is much lower than that of the other reported membranes.The enhanced selectivity of the as-fabricated pristine PEBAX membrane approves the high FFV and better polymerization of the polymeric lm. 74The gas permeability for PEBAX based mixed matrix membranes reveals that addition of inorganic llers to the polymeric lm does not always boost the membrane performance.Furthermore, they also may have a negative effect on the adhesion of the polymer on the surface of the llers which generates structural defects in the membrane.Furthermore, the addition of inorganic llers some time induces polymeric chain destruction, active functional group blockage, etc.

Conclusions
Nanostructure zeolite molecular sieves (zeolites A and Y) were synthesized for MMM fabrication.Pristine PEBAX membranes of different thicknesses have been fabricated and their single gas permeation performance, polymeric conformation, and chemical structure have been evaluated extensively.The diffraction, thermal and spectroscopic studies assert that solvent evaporation kinetics plays a signicant role in the observed polymeric conformation.Moreover, during evaporation, the polymeric lm remains in contact with the vapor of the solvent which signicantly affects the crystal structure of the resultant polymer.The single gas permeation results demonstrate the high potential of the reported polymeric structure optimization concept to signicantly enhance the gas permeability.The optimal 14 mm thickness P 14 membrane with high FFV shows very high CO 2 permeability (184.7 Barrer) as well as CO 2 /N 2 selectivity (59.7) at 2.7 bar and 25 C.This paper also demonstrates that the permeability, as well as CO 2 selectivity, can be improved by just reforming the polymeric structure without using any inorganic llers and surfactants.It reveals that the permeability and selectivity improvement is mainly attributed to changes in the polymer conformation and total free volume.Thus, by improving the polymeric structure of PEBAX as well as by reforming the free-volume in the membrane, pristine PEBAX lms can absorb CO 2 molecules more favorably than N 2 molecules.The pristine PEBAX membranes reported in this paper show even better performance than PEBAX based MMMs which encourages us to check the possibilities to fabricate high quality and greater CO 2 separation performance membranes.

Fig. 1
Fig. 1 Schematic diagram of the experimental set-up (time-lag machine) for the single gas permeation.

3. 1
Molecular sieve characterizationNano-molecular sieve zeolites A and Y of different Si/Al ratios, shapes, pore sizes and channel structures (Scheme 1) have been successfully synthesized using a microwave hydrothermal reactor.SEM micrographs (Fig.2a, b, S2, and S3, ESI †) of zeolite A and zeolite Y type molecular sieves show the formation of well-developed nanocrystals with a regular morphology.The zeolite A sample contains cube shaped nanocrystals of size around 55 nm, whereas the as-synthesized zeolite Y powder sample contains $40 nm octahedral crystals.The light scattering analysis (LSA) demonstrates the formation of uniform size crystals with narrow PSD (Fig.S4, ESI †).Moreover, Fig.S4(ESI †) reveals that the average size of zeolite A cubic crystals is 60 nm, whereas that of zeolite Y octahedrons is 45 nm.Although the light scattering analyses just provide primary information about the nature and size of particles, the PSD curves presented in Fig.S4 (ESI †) for zeolite molecular sieves are in good agreement with microscopic analyses reported in Fig.2a, b, S2, and S3, ESI.† Furthermore, the XRD patterns of zeolite A as well as zeolite Y (Fig.S5, ESI †) corresponded well with the earlier reported studies and JCPDS data le (LTA #97-002-4901 and FAU # 98-003-4277

Fig. 3
Fig.3Cross sectional SEM micrographs of various thickness PEBAX-1657 membranes.Magnified view of the surface and cross section of P 63A and P 56Y membranes revealing the presence of zeolite A and Y nano-particles in PEBAX/nano-molecular sieve MMMs.

Fig. 4
Fig. 4 XRD patterns of various thickness PEBAX-1657 membranes.Direction of doted arrows shows the increase in respective peak intensities.

Fig. 6
Fig. 6 Two different classes of crystal structures formulated with different polymeric chain packing schemes in nylon 6.Schematic representation of PEBAX polymerization, and hydrogen bonding among polymeric chains leads to a stable polymeric configuration, high crystallinity and enhanced FFV.

Fig. 7
Fig.7FTIR spectra of P 14 , P 22 , P 40 and P 75 PEBAX membranes.Inset spectra represent the variation in vibrational peaks in the range of 1200-1500 cm À1 .

Table 2
36nsity, FFV and SFV values of different thickness pristine PEBAX membranes As shown in TableS2(ESI †), the diffusion coefficient for CO 2 gas increases for pristine PEBAX membranes as the thickness decreases.The diffusion coefficient of CO 2 increases from nearly 1.2 Â 10 À6 cm 2 s À1 for P 75 to 2.6 Â 10 À6 cm 2 s À1 for P 14 pristine PEBAX membranes.The increase of FFV in both PEO and PA6 segments of pristine PEBAX membranes results in an enormous increase in CO 2 diffusivity.30Caretal.72reported a CO 2 diffusion coefficient of 4.6 Â 10 À7 cm 2 s À1 at 30 C and 600 mbar feed pressure.Kim et al.73determined a CO 2 diffusion coefficient of 1.52 Â 10 À6 cm 2 s À1 by using a continuous ow technique at 25 C and 3 atmosphere feed pressure.Furthermore, Wang et al.,30Xin et al.35and Reijerkerk et al.36reported CO 2 diffusion coefficients of 1.35 Â 10 À6 cm 2 s À1 , 1.43 Â 10 À6 cm 2 s À1 and 7.9 Â 10 À7 cm 2 s À1 for pristine PEBAX membranes, respectively.

Table 3
Pure gas permeation properties and permselectivity of the different thickness pristine PEBAX membranes