Gas-separation applications of miscible blends of isomeric polyimides

Blends of polyimide isomers containing hexafluoroisopropylidene in the central moiety of the diamine residue have been studied. The isomers differed by having either a meta or a para linkage between the diamine and dianhydride residues. The miscibility of these materials was investigated by studying the glass transition temperature behavior using differential scanning calorimetry. Mixtures of isomer pairs, such as 6FDA–6FmDA and 6FDA–6FpDA, exhibited one glass transition temperature. T_g, and were therefore miscible. Mixtures of nonisomer pairs exhibited two T_g's and were immiscible. The gas sorption and transport properties of the blends of the 6FDA–6FmDA and 6FDA–6FpDA isomers were characterized for a variety of gases at 35°C for pressures up to 60 atm. The permeabilities and permselectivities in the miscible blends fell between those of the pure components and were approximately logarithmic averages of the pure component properties. The miscibility of the polyimide isomers enables one to tailor the composition of the material to optimize the gas separation and mechanical properties. © 1993 John Wiley & Sons, Inc.     

Electro conductivities of well‐dispersed PMMA‐g‐MWNTs/6FDA‐based polyimide composites: Effect of chemical structure

PMMA (polymethylmethacrylate), which is miscible with hexafluoropropane dianhydride (6FDA)‐based polyimide, was grafted onto MWNTs surfaces to enhance their dispersion relative to that of pristine MWNTs. The electrical conductivity of the 6FDA‐based composite revealed percolation threshold behavior, and the 6FDA‐4,4′‐(hexafluoroisopropylidene)diamine, (6FpDA):3,5‐diaminobenzoic acid (DABA)/PMMA‐g‐MWNT composite showed a higher percolation threshold concentration and a slightly lower critical exponent compared with those of the 6FDA‐6FpDA composite. Because of the weak interaction energies between 6FDA‐6FpDA:DABA and PMMA, agglomerated domains were formed. Also, the weak interaction energies of the 6FDA‐6FpDA:DABA led to a larger reduction in the normalized transmittance compared with that seen in the 6FDA‐6FpDA composite. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Physical aging of thin 6FDA-based polyimide membranes containing carboxyl acid groups. Part I. Transport properties

The effect of molecular structure on the kinetics of physical aging of thin films (∼350 nm) formed from glassy 6FDA-based polyimides was investigated by tracking the changes in gas permeability (He, O₂ and N₂) at 35 °C for more than 2000 h. The structures studied included homopolymers of 6FDA with 6FpDA and with DAM plus copolymers where a portion of the latter two monomers was replaced with DABA to introduce carboxyl units into the structure for subsequent cross-linking studies. Over this period of aging, the oxygen permeability decreased by a factor of two for the polyimide containing the diamine 6FpDA and by a factor of five for the polyimide containing the diamine DAM. Introduction of DABA units accelerated the aging in the case of 6FpDA and slowed the aging in the case of DAM. Aging rate seems to correlate with the level of free volume of the polymer; the higher the free volume, the faster is the aging. Selectivity for all gas pairs increased upon aging but the rate is not simply explained by free volume alone because the difference in size of the two gas molecules is also reflected in the response to physical aging observed.     

Relationship between the gas transport properties and the refractive index in high‐free‐volume fluorine‐containing polyimide membranes

The refractive index and gas transport properties (i.e., permeability, diffusivity, and solubility) in the 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA)‐based polyimides were systematically investigated in terms of their polymer fractional free volumes (FFVs). The permeability and diffusion coefficients of the 6FDA‐based polyimide membranes to hydrogen, oxygen, nitrogen, methane, and carbon dioxide were correlated with their FFVs, which were estimated with van Krevelen's group contribution method. Linear correlations were also observed between the gas transport properties and the refractive index of these polyimides. We described FFV as a function of the refractive index based on the Lorentz–Lorenz equation. Linear correlations were observed between their refractive‐index‐based FFVs and the gas permeability, diffusivity, and solubility coefficients of these 6FDA‐based polyimides membranes. However, the FFVs of the 6FDA‐based polyimides calculated from refractive index were 1.16–1.37 times larger than their FFV values. This FFV was dependent on the free‐volume space and optical factors, such as the refractive index and molar refraction, which affected the electronic structure and the interactions between the gas molecules and the polymer segments. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and gas transport properties of novel hyperbranched polyimide–silica hybrid membranes

Physical and gas transport properties of hyperbranched polyimide (HBPI)—silica hybrid membranes prepared with a dianhydride monomer, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and triamine monomers, 1,3,5‐tris(4‐aminophenoxy)triazine (TAPOTZ), and 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), were investigated and compared with those of 6FDA‐TAPOB HBPI system synthesized from 6FDA and 1,3,5‐tris(4‐aminophenoxy)benzene (TAPOB). Glass transition and 5% weight‐loss temperatures of the 6FDA‐based HBPI–silica hybrid membranes were increased with increasing silica content. 6FDA‐TAPOTZ HBPI system, however, showed relatively low 5% weight‐loss temperatures, suggesting thermal instability of triazine‐ring in the TAPOTZ moiety. CO₂/CH₄ permselectivity of the HBPI–silica hybrid membranes were increased with increasing silica content, tending to exceed the upper bound for CO₂/CH₄ separation. This result indicated that free volume elements effective for CO₂/CH₄ separation were created by the incorporation of silica for the HBPI–silica hybrid systems. Especially, 6FDA‐TAPB HBPI system had high gas permeabilities and CO₂/CH₄ separation ability, arising from high fractional free volume and characteristic size and distribution of free volume elements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Gas‐sorption properties of 6FDA–durene/1,4‐phenylenediamine (pPDA) and 6FDA–durene/1,3‐phenylenediamine (mPDA) copolyimides

We investigated the sorption isotherms of O₂, N₂, CH₄, and CO₂ gases in 6FDA–durene, 6FDA–1,4‐phenylenediamine (6FDA–pPDA), and 6FDA–1,3‐phenylenediamine (6FDA–mPDA) homopolymers and 6FDA–durene/pPDA and 6FDA–durene/mPDA copolyimides. The solubilities decrease in the order of the inherent condensabilities of the penetrant gases, namely, CO₂, CH₄, O₂, and N₂. The chemical structures of the polymer, as well as the chain packing, determine the sorption properties of these homopolymers and copolymers. The FDA–durene homopolymer has the highest solubility for all gases because of its high specific free volume and fractional free volume. The solubilities of the copolymers increase with an increasing 6FDA–durene content, while the solubility selectivities of the copolymers only vary slightly. The values of K_D (Henry's law constant) and C_H′ (Langmuir site capacity) of these copolyimides decrease with a decreasing 6FDA–durene content. To our surprise, contradictory to the previous known fact that the meta‐connected materials tend to have denser molecular packing than that of the para‐linked materials for homopolymers, the 6FDA–durene/mPDA 80/20 copolymer has higher gas solubilities than those of the 6FDA–durene/pPDA 80/20 copolymer. The random moiety sequence within the copolymer may be the main cause for the abnormal phenomenon. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2187–2193, 2003     

Gas Permeation Properties of Copolyimides from 1,4-Bis(3,4-dicarboxyphenoxy)benzene Dianhydride and 2,2-Bis(3,4- dicarboxyphenyl)hexafluoroisopropane Dianhydride

A series of aromatic copolyimides was prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) and 2,2-bis(3,4-dicarboxy-phenyl)hexafluoroisopropane dianhydride (6FDA) with 3,3′-dimethyl-4,4′-methyl-ene dianiline (DMMDA) by a chemical imidization. The gas permeability coefficients of the copolyimides to H₂, CO₂, O₂, N₂ and CH₄ were measured under 7atm. pressure. The fractional free volume of 6FDA–DMMDA is larger than that of HQDPA–DMMDA, while the chain segmental mobility of 6FDA–DMMDA is lower than that of HQDPA–DMMDA. The gas permeability of 6FDA–DMMDA is much higher than that of HQDPA–DMMDA but the perm-selectivity of 6FDA–DMMDA for H₂, CO₂, O₂, N₂ over CH₄ is lower than that of HQDPA–DMMDA. The experimental values of the gas permeability coefficients of the copolyimides are in satisfactory agreement with the values estimated from the gas permeability coefficients of the constituent homopolyimides and their weight fractions. © of SCI.     

Free volume and permeabilities of O2 and H2 in Nafion membranes for polymer electrolyte fuel cells

The mechanism of gas permeation in Nafion membranes for polymer electrolyte fuel cells has been investigated from the viewpoint of free volume. Three different samples, a membrane with ionic exchange capacity (IEC) = 0.92 meq/g, and recast samples with IEC = 0.92 and 1.00 meq/g were used after drying. Free volume was quantified using the positron annihilation lifetime (PAL) technique and gas permeabilities were measured for O₂ and H₂ as functions of temperature and relative humidity. Good linear correlations between the logarithm of the permeabilities at different temperatures and reciprocal free volume indicate that gas permeation in dry Nafion is governed by the free volume. Nevertheless permeabilities are much smaller than the corresponding flexible chain polymer with a similar free volume size due to stiff chains of the perfluoroethylene backbone. In highly hydrated Nafion above 60% relative humidity, where the O₂ permeability varies oppositely to the free volume, gas permeation proved to be controlled by the gradual increase in overall flexibility of the Nafion–water system.     

Electrical properties of low density polyethylene/ZnO nanocomposites: The effect of thermal treatments

Low density polyethylene (LDPE)/ZnO nanocomposites were prepared by melt compounding followed by annealing or quenching treatment. Electrical properties of the thermally treated nanocomposites were investigated. The results showed that thermal treatments exerted a pronounced effect on the electrical properties of LDPE/ZnO nanocomposites. The dielectric constant of annealed LDPE/ZnO nanocomposites at various ZnO contents was higher than that of quenched nanocomposites. In sharp contrast, the resistivity of annealed LDPE/ZnO nanocomposites was considerably lower than that of quenched samples. The frequency dependence of dielectric constant was much pronounced for both the annealed and quenched LDPE/ZnO nanocomposites associated with the formation of ZnO network as the ZnO volume content reached 52 vol %. The structure–property relationship of the nanocomposites is discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1436–1444, 2006     

Mixed gas and pure gas transport properties of copolyimide membranes

Copolyimides were synthesized from dianhydride of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with various diamine contents of 4,4′‐oxydianiline (ODA) and 2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (TeMPD) by chemical imidization in a two‐step procedure. Polyimides (PIs) were characterized using thermogravimetric analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, as well as specific volume and free volume. The gas transport properties for pure gas and blends of CO₂ and CH₄ for the homopolymers and 6FDA‐ODA/TeMPD copolymers were investigated at 35°C and 150 psi pressure. In pure gas permeation, permeability of CO₂ and CH₄ increased with increasing TeMPD content in the diamine moiety, whereas the ideal selectivity decreased with increasing TeMPD content. In the mixed gas permeation, permeabilities and separation factor were measured as a function of CO₂ feed molar fraction for five PI membranes. The behavior of pure gas and mixed gas permeabilities and separation factor of CO₂/CH₄ mixtures as the chemical nature of the diamine and the CO₂ molar fraction in the feed gas were varied and are discussed in detail. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

A governing equation for physical aging of thick and thin fluoropolyimide films

An equation based on the segmental/chain mobility in free volume theory was derived to correlate the gas permeation coefficient and the aging time. An accelerated physical aging of a fluoropolyimide was observed and employed to validate this equation. A strong thickness‐dependent aging process was found by employing pure O₂ and N₂ tests to monitor the change of gas permeation properties as a function of aging time. Experimental results also suggest that chain rigidity and configuration play important roles in physical aging. As a result, the thin 2,2′‐bis(3,4′‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) based polyimide films studied here have different permeability versus time relationship from conventional polyarylate in the early stage of aging, and the experimental data seem to fit the proposed equation well. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1758–1764, 2004     

Effect of annealing on the permeation characteristics of gases of coextruded LLDPE films

The temperature dependence of both the permeability and diffusion coefficients of carbon dioxide, oxygen and nitrogen in annealed LLDPE films are studied. It is found that the values of the permeability coefficient through the annealed membranes are nearly four times larger than those through the non-annealed ones. The fact that annealing slightly diminishes the values of the diffusion coefficient leads to the conclusion that the rise in permeability detected in the films by effect of annealing should be attributed to an increase in solubility. The permeability characteristics of the films are interpreted in terms of the free volume theory.     

Synthesis,characterization, and CO2 permeation properties of acetylene‐terminated polyimide membranes

A novel fluorine‐containing telechelic polyimide end‐capped with acetylene group which derived from 4,4‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,4‐diaminodiphenyl ether (DADE), and 4‐(2‐phenylethynyl) phthalic anhydride (PEPA) was synthesized using polycondensation. The physical and CO₂ permeation properties of its crosslinked membranes prepared by the cyclotrimerization reaction of the acetylene groups at the polymer chain end using tantalum (V) chloride (TaCl₅) as a catalyst under thermal treatment was investigated in terms of CO₂‐induced membrane plasticization. The crosslinked membranes showed a gel content in organic solvent, which was good solvent of noncrosslinked membranes, and improved their thermal stability. Based on the measurement of the high‐pressure time dependence on CO₂ permeation, the crosslinked 6FDA–DADE–PEPA membranes exhibited more resistance to CO₂‐induced plasticization than noncrosslinked 6FDA–DADE and thermal treated 6FDA–DADE–PEPA. Furthermore, the increase in TaCl₅ content resulted in more resistance to plasticization. The cyclotrimerization reaction of the acetylene groups at the polymer chain ends using a transition metal catalyst under thermal treatment was found to be more effective than conventional thermal treatments for suppressing membrane plasticization without the membrane densification. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Gas transport properties in (6FDA‐RTIL)‐(6FDA‐MDA) block copolyimides

This article reports synthesis and structure property studies of block copolyimides synthesized using diamino room temperature ionic liquids (RTIL) as diamine monomers. Specifically, polyimide oligomers of different lengths were synthesized using 2,2‐bis (3,4‐carboxylphenyl) hexafluoropropane dianhydride (6FDA) and diamino RTIL (1,3‐di(3‐aminopropyl) imidazolium bis[(trifluoromethyl) sulfonyl] imide). These oligomers were copolymerized with 6FDA and m‐phenylenediamine (MDA) using in situ polymerization to form (6FDA‐RTIL)‐(6FDA‐MDA) block copolyimides. The impact of the length and relative concentration of 6FDA‐RTIL oligomer in the copolymer on the resulting thermal, physical, and gas transport properties was monitored. As the concentration of the 6FDA‐RTIL segments increased, the backbone of the block copolyimides became more flexible resulting in a decrease in the glass transition temperature (T_g) and an increase in the density. The permeabilities of the RTIL containing copolyimides were consistently lower than those of the base polyimide, 6FDA‐MDA, with some increase in selectivities. Interestingly, the permeabilities of films produced with the low molecular weight oligomers were very different than those produced with same composition of the high molecular weight oligomers. This may be indicative of very different morphologies within these copolyimides. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43077.     

Morphology and physical properties of nanocomposites based on poly(methyl methacrylate)/poly(vinylidene fluoride) blends and multiwalled carbon nanotubes

Nanocomposites of blends of poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) with multiwalled carbon nanotubes (CNTs) were prepared by melt mixing and hot press molding followed by quenching or annealing (120°C, 24 h). PMMA‐rich nanocomposites showed higher electrical conductivity than PVDF‐rich samples at identical CNT loading. At a specific composition, the quenched nanocomposites showed electrical conductivity values three to four orders of magnitude higher than those observed in annealed samples. Measurement of the dielectric constants also supported the electrical conductivity results. In the annealed samples, agglomerated CNTs located mainly in the PVDF crystalline phase were observed. Addition of CNTs promoted the crystallization, and especially, the formation of β‐crystals, which was confirmed by X‐ray diffraction. The thermal behavior of nanocomposites from differential scanning calorimetry (DSC) analysis was explained in terms of the three‐phase model involving the presence of the rigid amorphous fraction, the mobile amorphous fraction, and the crystalline phase. POLYM. COMPOS., 36:1195–1204, 2015. © 2014 Society of Plastics Engineers     

Gas permeability of polyimides and polypyrrolone derived from 2,2′-bis(p-trimellitoxyphenyl)hexafluoropropane dianhydride

The permeability coefficients for H₂, O₂, and N₂ in four polyimides and one polypyrrolone based on 2,2′-bis(p-trimellitoxyphenyl)hexafluoropropane dianhydride were determined at 30°C and 1 atm. Systematic variations in chemical structure were found to lead to significant changes in permeabilities and selectivities. The relationship between the chemical structure of the polymers, some of their physical properties (d-spa+ing, fractional free volume), and their gas permeability behavior are discussed. Introduction of 2 flexible segments tends to increase permeability but decrease selectivity. Structural moieties, which simultaneously inhibit chain packing and intrasegmental mobility, may increase permeability while maintaining selectivity. Temperature dependency of gas permeabilities was also reported for polypyrrolone. © 1996 John Wiley & Sons, Inc.     

Impact of H+ ion beam irradiation on Matrimid®. II. Evolution in gas transport properties

Ion beam irradiation is an easily controlled method to modify the chemical structure and microstructure of polymers including the fractional free volume, free volume distribution and chain mobility, thus altering the gas transport properties of the irradiated polymers. The previous paper focused on the impact of H⁺ ion beam irradiation on chemical structural evolution of the polyimide Matrimid®. This paper focuses on the impact of H⁺ ion beam irradiation on microstructure and gas permeation properties of Matrimid®. Irradiation at low ion fluence resulted in slight decreases in permeabilities for five gases (i.e., He, CO₂, O₂, N₂, and CH₄) with increases in permselectivities for some gas pairs (e.g., He/CH₄ and He/N₂). In contrast, irradiation at relatively high ion fluences resulted in simultaneous increases in permeabilities and permselectivities for most gas pairs (e.g., He/CH₄, He/N₂, O₂/N₂, and CO₂/CH₄). While Matrimid® has bulk gas permeation properties that are below the range of commercially interesting polymers, samples irradiated at high ion fluences exhibited significant improvement in gas separation performances. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1670–1680, 2007     

Oxygen stoichiometry,chemical expansion or contraction,and electrical properties of rutile,TiO2±δ ceramics

Rutile, TiO₂ is increasingly oxygen-deficient on heating in air above ~700°C. The weight loss is generally too small for accurate measurement, but the electrical properties of quenched samples provide a sensitive qualitative indicator of oxygen content since their conductivity can vary by many orders of magnitude. The oxygen lost at high temperature is fully recovered if samples are cooled slowly. With rapid quenching, by dropping samples into liquid N₂, the oxygen stoichiometry at high temperature is preserved to ambient and the resulting materials are kinetically stable but thermodynamically metastable. The lattice parameters of quenched samples showed an unusual dependence on quench temperature and, by implication, on oxygen stoichiometry. Lattice parameters increased with a small oxygen loss, δ; chemical expansion of the lattice occurred and is attributed to reduction in average Ti oxidation state and increase in Ti–O bond lengths. At higher δ, lattice parameters started to decrease giving a chemical contraction effect attributed to partial collapse of columns of edge-sharing TiO₆ octahedra in the rutile structure and elimination of oxygen vacancies by crystallographic shear plane formation. Oxygen-deficient samples quenched from above 700°C were n-type, as were samples annealed and measured at 650 and 700°C. Samples measured at 450-500°C were p-type and believed to be slightly oxygen-rich; it is suggested that holes located on oxide ions at or near the sample surface arose from redox electron transfer between underbonded surface oxide ions and adsorbed O₂ molecules. Samples annealed between 550 and 600°C showed cross-over between n- and p-type behavior.     

Hybrid organic inorganic nylon‐6/SiO2 nanocomposites: Transport properties

Organic‐inorganic hybrid membranes of nanosized SiO₂‐filled polyamide composites were prepared via film casting and their transport properties were studied. Gas permeation measurements were performed at room temperature, and the membrane exhibited an increase in membrane permeability performance. In contrast to the performance of traditional dense filled polymer systems, the permeability increased with an increased number of nanosilica particles. The nanocomposites were studied using positron annihilation lifetime spectroscopy (PALS). From the ortho‐positronium (o–Ps) lifetime (τ₃), the size of the local free volume (holes) was estimated. The increase in permeability is ascribed to the additional free volume obtained. This is created by the presence of nanoparticles that alter the PA chain packing. Furthermore, wide angle X‐ray diffraction (WAXD) patterns revealed that the incorporation of silica induced the structural modification of polymer chains by modifying the degree of crystallinity in comparison with the neat polymer. Polym. Eng. Sci. 44:1240–1246, 2004. © 2004 Society of Plastics Engineers.     

Aging behavior of oxygen plasma-treated polypropylene with different crystallinities

Oxygen plasma-treated quenched and annealed polypropylene (PP) films with different crystallinities were investigated to characterize the surface rearrangement behavior during aging using contact-angle measurements and X-ray photoelectron spectroscopy. Optimum plasma conditions were examined by varying the power, time and pressure. Less crystalline quenched PP showed a larger increase in water contact angle and a larger decrease of oxygen atomic concentration during aging than the more crystalline annealed PP, since the oxygen species, such as hydroxyl groups, introduced by oxygen plasma treatment, oriented towards or diffused faster into the bulk with lower crystallinity. The degree of crosslinking on the surface was enhanced after plasma treatment and, in addition to increased crystallinity, the crosslinked structure induced by plasma treatment restricted chain mobility and lowered the aging rate of the PP surface.