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A series of mixed matrix membranes (MMMs) based on polyurethane (PU) and silica nanoparticles was fabricated. Three types of PU were synthesized with different polyethylene glycol (PEG)/polytetramethylene glycol ratios (PU0, PU75, and PU100, the corresponding numbers: PEG percent). The MMMs were characterized using FTIR, SEM, and gas permeation measurements (N2, O2, CH4, and CO2). The phase mixing of PU0 and PU75 membranes increased with silica content. This resulted in a decrease in gas permeability, while an increase in CO2/CH4 and CO2/N2 selectivities. The gas separation trend for PU100 membranes was the opposite. The molecular probing approach was served to study the interfacial structure of the MMMs. The existence of a rigidified polymer layer with 2.38 and 2.44 nm thicknesses around silica was revealed through PU0 and PU75 membranes, respectively. In contrary, silica was surrounded by a polymer chain dilution interphase with a thickness of 2.20 nm for PU100 MMMs. [ABSTRACT FROM AUTHOR]

A series of polysulfone (PSF) membranes were prepared using different solvents: dimethylformamide (DMF), tetrahydrofuran, dimethylacetamide, and n‐methyl‐2‐pyrrolidone (NMP). The PSF membrane prepared by NMP showed the highest gas permeability. The influence of propionic acid as a Lewis acid on gas separation properties of the PSF was explored. The PSF membrane prepared by the casting solution containing 25 wt% PSF, 35 wt% propionic acid, and 40 wt% NMP showed a superior gas separation performance. The gas permeation measurements indicated that incorporating 30 wt% γ‐alumina nanoparticles into the PSF matrix resulted in about the respective 43% and 41% increase in CO2 and O2 permeability together with a rise in CO2/CH4 and O2/N2 selectivities (13% and 7%, respectively). Furthermore, by rearranged modified Maxwell model, the role and nature of the interfacial layer in the PSF‐based mixed matrix membranes were mathematically analyzed considering a reduced permeability factor. [ABSTRACT FROM AUTHOR]

The increasing need for more efficient separation processes has motivated the development of polymer membranes that can provide fast and selective transport. In this work, cadmium‐based metal–organic framework (MOF) nanoparticles and a polyurethane–urea (PUU) elastomer were synthesized. New mixed‐matrix membranes (MMMs) were then fabricated from the nanoparticles and the PUU. SEM images verified that embedding the nanoparticles changes the morphology of the PUU and the nanoparticles disperse well in the PUU due to satisfactory compatibility of the polymer and nanoparticles. Fourier transform infrared spectroscopy and X‐ray diffraction analysis confirmed the dispersion of the nanoparticles in the soft segment of the PUU. With increased temperature, gas permeabilities of the MMMs improved but their sieving ability deteriorated. An MMM incorporating 2.5 wt % of the MOF showed a CO2 permeability of ~140 barrer and a CO2/N2 selectivity of ~30, which are 89 and 38% higher than those of the pristine membrane. Gas permeation tests showed that the higher CO2/N2 selectivity of the MMMs was due to improved solubility selectivity and the higher CO2 permeability was a result of improved CO2 diffusivity and solubility coefficients. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 137, 48704. [ABSTRACT FROM AUTHOR]

The separations of ethylene/ethane and propylene/propane using polysulfone‐silica nanocomposite membranes were studied. Silica nanoparticles were prepared via sol‐gel method and the membranes by phase inversion. Characterization by Fourier transform spectroscopy and scanning electron microscopy indicated a good distribution of silica nanoparticles in the polymer matrix and also a good compatibility between the two phases. The performances of the prepared membranes in ethylene‐ethane and propylene‐propane separation were evaluated. The results showed the increments in gas permeability and selectivity by silica. Higher silica contents increased the solubility coefficient and reduced the diffusion coefficient of gases. The plasticization pressure of polysulfone was increased by incorporating the silica nanoparticles in polymer. [ABSTRACT FROM AUTHOR]

Polymer/nanoparticle mixed matrix membranes (MMMs) is one of the most important topics in gas separation field. In this study, to improve gas separation efficiency, methoxy poly(ethylene glycol) methacrylate (MPEG) was grafted on TiO2 surface and was used for synthesis of poly (methyl methacrylate) (PMMA) MMMs. Gas permeation and separation properties of PMMA/PMPEG-TiO2 MMMs were studied for CO2, CH4, O2, and N2 gases. The results showed that the MMM filled with 5 wt% PMPEG-TiO2 nanoparticle exhibited optimal separation performance with CO2 permeability of 32.48 Barrer and CO2/N2 selectivity of 56.98, which are higher than pure polymer (2.75 Barrer and 36.71). [ABSTRACT FROM AUTHOR]

Abstract A series of poly(urethane-urea) (PUU) membranes based on contributing hard segments in gas separation were prepared using two novel bulky chain extenders, polytetramethylene-glycol, isophorone and hexamethylene-diisocyanate. The chain extenders were synthesized by cyanuric chloride, aniline/naphthylamine and hydrazine. According to FTIR, AFM and DSC, bulkier PUU membranes showed more phase separation and lower glass transition temperature consistent with higher fractional free volume, which were correlated with single (CO 2 , CH 4 , O 2 and N 2) and mixed (CO 2 :N 2 and CO 2 :CH 4) gas permeation results. The main findings indicate these polyurethanes serve efficiently designed molecular structures favoring bulky hard segments contribution in gas separation. The bulky PUU membranes afford simultaneous increased permeability and selectivity, while maintaining high tensile properties. Enhanced O 2 /N 2 diffusivity selectivity by bulkier PUU and CO 2 sorption/desorption study by Ellipsometry confirmed hard segments' association, too. The bulkiest membrane provided 126% and 54% improvement for single CO 2 permeability and CO 2 /N 2 selectivity compared to linear one. Graphical abstract fx1 Highlights • A series of PUU membranes were prepared based on two novel bulky chain extenders. • The synthesized chain extenders and PUUs characterized completely. • The gas separation, physical and mechanical properties of bulky PUUs were evaluated. • Association of hard segments and enhancement on gas separation properties was shown. • High gas permeability/selectivity and high mechanical strength afforded in bulky PUUs. [ABSTRACT FROM AUTHOR]

The concept of mixed matrix membrane comprising dispersed inorganic fillers into a polymer media has revealed appealing to tune the gas separation performance. In this work, the membranes were prepared by incorporation of mesoporous silica into polyurethane (PU). Mesoporous silica particles with different pore size and structures, MCM‐41, cubic MCM‐48 and SBA‐16, were synthesized by templating method and functionalized with 3‐aminopropyltriethoxysilane (APTES). High porosity and aminated surface of the mesoporous silica enhance the adhesion of the particles to the PU matrix. The SEM and FTIR results showed strong interactions between the particles and the PU chains. Moreover, the thermal stability of the hybrid PUs improved compared to the pure polymer. Gas transport properties of the membranes were measured for pure CO2, CH4, O2, and N2 gases at 10 bar and 25°C. The results showed that the gas permeabilities enhanced with increasing in the loading of modified mesoporous silica particles. High porosity and amine‐functionalized particles render opportunities to enhance the gas diffusivity and solubility through the membranes. The enhanced gas transport properties of the mixed matrix membranes reveal the advantages of mesoporous silica to improve the gas permeability (CO2 permeability up to ~70) without scarifying the gas selectivity (α(CO2/N2)~ 30 for 5 wt% SBA‐16 content). [ABSTRACT FROM AUTHOR]

Poly (ethylene glycol) (PEG)-based polyurethane (PU) membranes are attractive materials for CO 2 separation from various sources such as flue gas and syngas. However, the strong tendency of PEG chains to crystallize leads to reduced permeability of the membrane. Here, we developed new types of PU chemistries with high PEG content and reduced crystallinity. A series of PUs were synthesized based on mixtures of PEG and poly (propylene glycol) (PPG), and various PEG-PPG triblock copolymers (PEG-b-PPG). The presence of PEG-b-PPG triblock copolymers combines the high selectivity of PEG while the PPG pendant methyl group hinders local crystallization. The resulting membranes showed CO 2 permeability of 144 barrer and high CO 2 /N 2 and CO 2 /H 2 selectivities up to 54 and 8.3, respectively. Due to the absence of the crystalline soft phase, synthesized PUs with PEG-b-PPG triblock copolymers exhibit higher chain flexibility which is reflected by a decrease in the glass transition temperature of the soft segments. In contrast, the mixture of PEG and PPG showed minimal effects on the crystallinity of PEG domains. This resulted in lower membrane gas separation performance where CO 2 permeability and CO 2 /H 2 selectivity decreased to 68 barrer and 4.9, respectively. [ABSTRACT FROM AUTHOR]

Interfacial properties play an important role in determining characteristics and performance of composite materials, especially in membrane gas separation applications. Formation of any undesirable defect at polymer-particle interface can directly influence on membrane permeability and selectivity in addition to unwanted effects on the other mechanical/physical properties. For achieving a quick insight about the role and nature of interfacial morphologies in mixed matrix membranes (MMMs) and their effects on gas transport properties, a new technique mainly in terms of mathematical modeling was developed. Based on the proposed approach, although ideal models often failed in predicting MMMs performance, these models can provide guidelines for discernment of the types of formed interfacial morphology, like current methods in characterization. [ABSTRACT FROM AUTHOR]

This study involves the preparation and characterization of polyurethane (PU) and polyurethane/poly(ether-block-amide) (PU/PEBA) blend membranes for gas separation. Polyurethane was synthesized by two-step polymerization based on isophorone diisocyanate (IPDI), polytetramethylene glycol (PTMG2000), 1,4-butanediamine (BDA) and 1,4-butanediol (BDO) in mole ratios of 3:1:2. Two kinds of PEBA, MV3000 and MH1657, were chosen to prepare PU/PEBA blend membranes. The effects of the blend composition on the permeability of N 2 , O 2 , CO 2 and CH 4 were investigated. All membranes were prepared by thermal phase inversion. Physical properties of synthesized polyurethane and prepared blend membranes were investigated by FT-IR, XRD and SEM analyses. FT-IR results indicate that phase separation of hard and soft segments decreased as the amount of PEBA in blend membranes increased. XRD results demonstrate that crystallinity rose by increasing the amount of PEBA in the blends. According to the SEM micrographs of the prepared samples, PU/PEBA blend membranes are miscible systems. The results of gas permeation experiments demonstrate that by increasing the amount of PEBA in PU/PEBA blend membranes, the permeability of all gases decreased while selectivity increased. [ABSTRACT FROM AUTHOR]

Abstract: The effect of silica nanoparticles on the gas permeation properties of polycaprolactone-based polyurethane membranes was investigated. Polyurethane and polyurethane-silica nanocomposite membranes were prepared by solution blending and casting-evaporation methods. Silica nanoparticles were prepared by sol–gel method using hydrolysis of tetraethoxysilane (TEOS). Polyurethane was synthesized by bulk two-step polymerization, including polycaprolactone 2000(PCL)/hexamethylene diisocyanate (HMDI)/1,4-butanediol (BDO). The homogeneity and nano scale distribution of the prepared polyurethane-silica membranes were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and thermal gravimetric analysis (TGA). Gas permeation properties of these membranes with different silica contents, was studied for pure CO2, CH4, N2 and O2 gases. The results showed reduction in gas permeability, but enhancement in CO2/N2, CO2/CH4 and O2/N2 ideal selectivity. Also the effect of temperature and pressure on permeation properties of these membranes was investigated. The modified Higuchi model was applied to predict the permeability of polyurethane-silica nanocomposite membranes. Good agreement between the experimental data and the predicted gas permeability was obtained. [Copyright &y& Elsevier]

Abstract: This work presents the structural properties of gas permeation of a group of polyurethane membranes. All polymers were synthesized using a 1:3:2 molar ratio of polyol:diisocyanate:chain extender. The obtained results from Fourier transform infrared spectrometer (FT-IR) of polymers indicate that by changing the diisocyanate from aromatic to linear aliphatic, the microphase separation of hard and soft segments increases. Study of the differential scanning calorimetery (DSC) and X-ray diffraction (WAXD) patterns confirmed that PTMG and PCL polyols can be arranged in small crystalline structures. Furthermore, a hard ordered segment in crystal phase could be obtained, owing to the high phase separation of the polymer based on HDI. Permeation measurements of polymers revealed that the permeability of gases increases with microphase separation in polymer and selectivity of gases drops down. Polymers based on PPG showed the highest phase separation and permeability. The obtained results revealed more phase mixing of the polymer based on DMPA chain extender in comparison to BDO, which lead to lower permeability and higher selectivity. The solubility and diffusivity of gases indicate solubility domination of gas transport in these membranes. The observed solubility domination increases by phase separation. The results of permeability tests indicate high permeability, up to 186Barrer (1Barrer=1×10−10 [cm3 (STP) cm/cm2 scmHg]), and high selectivity for carbon dioxide with respect to nitrogen (CO2/N2: 45). Our data sheds light on gas permeation properties of polyurethane membranes. [Copyright &y& Elsevier]

Abstract: The effect of urethane and urea contents on gas separation properties of the groups of polyurethane–urea membranes is studied. The membranes used in this study were prepared by polytetramethylene-glycol (PTMG) and isophorone diisocyanate (IPDI) prepolymers. The prepolymers were converted to final polymer using the designed proportion of 1,4-butane diol (BDO) and 1,4-butane diamine (BDA) as a chain extender. Five different BDO/BDA ratios were chosen in order to synthesize poly(urethane-urea)s with different urethane/urea linkage content. The prepared polymers were characterized and the permeability of gases through them was investigated. Results obtained by Fourier transform infrared spectrometer (FT-IR) and differential scanning calorimetery (DSC) indicate that by increasing the urea linkage in the polymers, the microphase separation of hard and soft segments increase. Study of the X-ray diffraction (WAXD) patterns confirmed that polyols may be arranged in small crystalline structures. Permeation measurements of polymers revealed that the permeability of gases decreases with increasing urethane content in the polymers and selectivity of gases decreases with increasing urea content. The solubility and diffusivity of gases indicate solubility domination of gas transport in these membranes. The results of permeability also show high amounts up to 128Barrer (1Barrer=1×10−10 [cm3 (STP) cm/cm2 scmHg]), and high selectivity for carbon dioxide with respect to nitrogen (CO2/N2: 27). [Copyright &y& Elsevier]

Abstract: In the present work, the effect of silica nano particles on the permeability of CO2, CH4 and N2 gases in polybenzimidazole (PBI) membranes has been studied. Silica particles were prepared via the sol–gel method through the hydrolysis of tetraethoxysilane (TEOS). PBI and PBI–silica hybrid membranes were prepared by thermal phase inversion method. Scanning electron microscopy (SEM), X-ray diffraction and FTIR analyses were employed in order to characterize the PBI and PBI–silica composite membranes. The obtained SEM micrographs confirmed the nano-scale distribution of silica particles in the polymer matrix. Gas permeation experiments showed an increase in the solubility and a corresponding reduction in the diffusivity of the gases through the membranes by increasing the silica content in the polymer matrix; consequently, the permeability of the condensable CO2 and CH4 gases were enhanced whereas that of non-condensable N2 gas significantly decreased upon increasing the silica content of the nano-composite membranes. The permeability of CO2 and its selectivity over N2 was increased from 0.025Barrer and 3.5 in pure PBI to 0.11Barrer and 71.3 in the nano-composite containing 20wt% of the silica particles. There was a strong correlation between the solubility coefficients and condensability of the gases, as well as the diffusion coefficient of the penetrants and their kinetic diameter. Higuchi model fitted fairly well with the experimental results concerning the permeability of nitrogen gas in nanocomposite membranes, supposing the K H =3.8. [Copyright &y& Elsevier]

Abstract: The gas separation properties of ethylene vinyl acetate (EVA) membranes containing 18 and 28wt% of vinyl acetate (VA) were investigated in this study. The effects of membrane preparation conditions, such as thermal and thermal/wet phase inversion, and the type of solvent on the gas separation properties of EVA membranes were investigated. The permeation of pure O2, N2, CH4, and CO2 gases at different feed pressures ranging from 2 to 11 bar were examined. The results indicated that the CO2 permeability was evidently higher than those of the other gases. Furthermore, the solubility mechanism was found to be the dominant mechanism for permeation of gases through EVA membranes. Moreover, the membranes prepared using tetrahydrofuran (THF) as solvent showed higher gas permeabilities than those prepared using chloroform (CHCl3) as solvent. The results indicated that the gas permeabilities through membranes prepared using wet phase inversion technique were higher. Also, the membranes prepared by thermal/wet phase inversion method at higher temperatures showed improved gas separation properties. In addition, the membrane with higher VA content prepared using THF as solvent presents higher gas separation properties. Trade-off evaluation also showed that certain types of the prepared EVA membranes in this study have potential for commercialization. [Copyright &y& Elsevier]

In this study, TiO2 nanoparticles were functionalized by grafting polymerization of methoxy poly(ethylene glycol) methacrylate (MPEG) onto the nanoparticle surface. Functionalized TiO2 nanoparticle was used as nanofiller to prepare poly(vinyl alcohol) (PVA) based nanocomposite (NC) membranes through solution mixing method. The thermal and mechanical properties of PVA/PMPEG-TiO2 membranes were improved compared to pristine PVA membrane due to well dispersion and high compatibility between the inorganic fillers and the polymer matrix. Gas permeation and selectivity properties of PVA/PMPEG-TiO2 NC membranes with various TiO2 contents were also studied for O2, N2, CH4 and CO2. Gas permeability improvement was seen for studied gases, especially for CO2. In addition, the results showed higher CO2/N2 selectivity up to 49.36% for 3 wt% TiO2 containing NC membranes. [ABSTRACT FROM AUTHOR]

Polyurethanes (PUs) and polyurethane-ureas (PUUs), with good mechanical stability and the possibility of tuning the gas transport properties are promising materials for selective gas separation membranes. Here, we synthesized various types of PUs and PUUs with polytetramethylene glycol (PTMG), isophorone diisocyanate (IPDI) and different ethereal chain extenders (1:3:2 M ratio). FTIR and DSC results showed that the phase separation would vary in PUs and PUUs structures by changing the length and functionality of the chain extenders. More mixing was inferred for PUs and PUUs with high ethereal content. In contrast, phase separation was more likely with increases in the chain extender length. Pure (CO 2 , CH 4 , O 2 and N 2 ) and mixed gas (CO 2 :N 2 (50:50 vol%) and CO 2 :CH 4 (50:50 vol%)) permeation measurements correlated well with the phase separation in the polymer structure. The octanediamine-based PUU with the highest amount of phase separation showed the highest permeability (160 barrer for CO 2 and CO 2 /N 2 selectivity of 30). On the other hand, the 3,6-dioxa- 1,8-octanediol- based PU, despite having the same chain extender length as octanediamine-based PUU, presented the lowest phase separation and gas permeability (62 barrer for CO 2 and CO 2 /N 2 selectivity of 29). [ABSTRACT FROM AUTHOR]

• Surface modified silica nanoparticles with hyperbranched structure were prepared. • The mixed matrix membranes were prepared based on two types of poly(urethane-urea)s. • The silica impressed the phase segregation and chain mobility of the membranes. • CO 2 permeability and all selectivities of membranes increased up to 5 wt% loading. • 5 wt% loaded membranes provided the highest CO 2 capture and mechanical properties. Two types of poly(urethane-urea)-based mixed matrix membranes containing hyperbranched structures of surface-modified silica nanoparticles were fabricated. The stepwise surface modification of nanoparticles was done based on aminopropyltriethoxysilane, cyanuric chloride, and ethylenediamine. FTIR, TGA, elemental analysis, and SEM-EDX were served to characterize the modified particles. The incorporation of the nanoparticles into poly(urethane-urea)s (PUUs) altered the phase separation degree of soft and hard segments, elevated the glass transition of soft segments and reduced the chain order. MMM containing the optimal distribution of 5 wt% modified silica showed improved mechanical and gas separation properties with 20–25% and 30–36% enhancement in CO 2 permeability and CO 2 /N 2 selectivity, respectively. The presence of long adsorbent chains with NH moieties on the particles improves the particle distribution in the matrix, thereby enhanced CO 2 permeability up to 5 wt% particle content. At higher loadings, the agglomeration of the particles led to the formation of non-selective channels for gas diffusion and reduced gas separation performance and mechanical properties. [ABSTRACT FROM AUTHOR]