Copolyimide Brushes as a Component of a Hybrid Poly(phenylene Oxide) Membrane for Controlling Gas Separation: Effect of Water, Methanol, and Hexane Vapors.

The effect of water, methanol, and hexane vapors on gas permeability was studied in a hybrid membrane containing 5 wt% copolyimide brushes with poly(methyl methacrylate) side chains (PI-g-PMMA) in a poly(phenylene oxide) (PPO) matrix, and in a pristine PPO membrane. These membranes in the form of dense nonporous films were further examined by atomic force microscopy (AFM) and scanning electron microscopy (SEM), as well as by measuring their mechanical and gas transport properties. A gas separation study of the membranes in a dry state and the membranes saturated with water, methanol, and hexane vapors was performed to estimate the effect of each vapor on the H2, CO2, N2 permeability and selectivity in the separation of H2/N2 and CO2/N2 pairs. In general, saturation with water, methanol, and hexane vapors caused a decrease in the gas permeability of both membranes. The hybrid membrane containing copolyimide brushes demonstrated enhanced selectivity in the separation of H2/N2 and CO2/N2 pairs. It was found that a special effect of the vapors used for membrane saturation is associated with their molar volume. The solubility and diffusion coefficients of N2 and CO2 were obtained by Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations.

The Effect of Complex Modifier Consisting of Star Macromolecules and Ionic Liquid on Structure and Gas Separation of Polyamide Membrane.

A novel hybrid membrane was developed on the basis of poly(m-phenylene isophthalamide) (PA) by introducing an original complex modifier into the polymer; this modifier consisted of equal amounts of heteroarm star macromolecules with a fullerene C60 core (HSM) and the ionic liquid [BMIM][Tf2N] (IL). The effect of the (HSM:IL) complex modifier on characteristics of the PA membrane was evaluated using physical, mechanical, thermal, and gas separation techniques. The structure of the PA/(HSM:IL) membrane was studied by scanning electron microscopy (SEM). Gas transport properties were determined by measuring He, O2, N2, and CO2 permeation through the membranes based on PA and its composites containing a 5 wt% modifier. The permeability coefficients of all gases through the hybrid membranes were lower than the corresponding parameters for the unmodified membrane, whereas the ideal selectivity in the separation of He/N2, CO2/N2, and O2/N2 gas pairs was higher for the hybrid membrane. The position of the PA/(HSM:IL) membrane on the Robeson's diagram for the O2/N2 gas pair is discussed.

Novel Design of Co-Poly(Hydrazide Imide) and Its Complex with Cu(I) for Membrane Separation of Methanol/Dimethyl Carbonate Mixture.

Poly(2,2'-biquinoline-6,6'-dicarbohydrazide)-co-(bistrimelliteimide)methylene-bisanthranylide (PHI) and its metal-polymer complex PHI-Cu(I) containing several types of functional groups (hydrazide, carboxyl, amide, and imide fragments) were synthesized to prepare two types of dense nonporous membranes. The study on morphology using scanning electron microscopy (SEM), measurements of mechanical, thermal, and transport properties of the membrane samples was carried out. The main mechanical properties of both membranes do not differ significantly, but the values of ultimate deformation differ palpably as a result of a non-uniform character of the deformation process for the PHI membrane. The thermal analysis based on the curves of thermogravimetric (TGA) and differential thermal (DTA) analyses of the PHI and PHI-Cu(I) membranes revealed peculiarities of the membrane structure. Transport properties were studied in pervaporation (PV) of methanol (MeOH) and dimethyl carbonate (DMC) mixtures including an azeotropic point. Intrinsic properties of the penetrant-membrane system were also determined. It was found that the total flux is higher through the PHI membrane, but the PHI-Cu(I) membrane exhibits a higher separation factor. Calculation of the pervaporation separation index (PSI) allowed to conclude that the PHI-Cu(I) membrane exhibits better transport properties as compared with the PHI membrane.

Application of Cyclized Polyacrylonitrile for Ultrafiltration Membrane Fouling Mitigation.

In this study, novel composites were produced by blending partially cyclized polyacrylonitrile (cPAN) and poly(amide-imide) (PAI) in N-methylpyrrolidone in order to fabricate asymmetric membranes via phase inversion method. The compatibility of PAI and cPAN through possible intermolecular interaction was examined by quantum chemical calculations. The composite membranes were characterized by FTIR, SEM, contact angle measurements, etc. A considerable reduction in the contact angles of water and ethylene glycol (EG) was observed after adding cPAN to the PAI membrane, which is evidence of improved membrane hydrophilicity. Membrane transport properties were investigated in ultrafiltration tests by measuring the pure water flux, rejection of proteins, and flux recovery ratio (FRR). The best properties were found for the membrane containing 5 wt% cPAN; an increase in BSA rejection and a remarkable increase in FRR were observed, which can be explained by the hydrophilization of the membrane surface provided by the presence of cPAN.

Effect of ionic liquid on formation of copolyimide ultrafiltration membranes with improved rejection of La3.

Ultrafiltration (UF) as a widely used industrial separation method with optimal selection of membrane materials can be applied to extract rare earth metals from dilute solutions formed during the processing of electronic waste by hydrometallurgical methods. In the present work, promising UF copolyimide membranes were prepared using [hmim][TCB] ionic liquid (IL) co-solvent which can be considered as an environmentally friendly alternative to conventional solvents. The membranes were characterized by ATR-FTIR, TGA, SEM and quantum chemical calculations. A significant difference in morphology of these membranes was revealed by SEM of membrane cross-sections; the P84 membrane has finger-like structure of porous substrate in contrast to spongy structure of substrate for the P84/IL membrane due to a higher dynamic viscosity of the casting solution. The transport parameters were determined in ultrafiltration tests with pure water and an aqueous solution of bovine serum albumin. The addition of ionic liquid to the P84 casting solution increases the performance of the membrane. The rejection capacity was evaluated with respect to La3+ in the form of a lanthanum alizarin complex (LAC) in aqueous acetone solution. The P84 membrane prepared using IL showed a high rejection (98.5%) with respect to LAC, as well as a significant productivity.

A Review of Recent Developments of Pervaporation Membranes for Ethylene Glycol Purification.

Ethylene glycol (EG) is an essential reagent in the chemical industry including polyester and antifreeze manufacture. In view of the constantly expanding field of EG applications, the search for and implementation of novel economical and environmentally friendly technologies for the separation of organic and aqueous-organic solutions remain an issue. Pervaporation is currently known to significantly reduce the energy and resource consumption of a manufacturer when obtaining high-purity components using automatic, easily scalable, and compact equipment. This review provides an overview of the current research and advances in the pervaporation of EG-containing mixtures (water/EG and methanol/EG), as well as a detailed analysis of the relationship of pervaporation performance with the membrane structure and properties of membrane materials. It is discussed that a controlled change in the structure and transport properties of a membrane is possible using modification methods such as treatment with organic solvents, introduction of nonvolatile additives, polymer blending, crosslinking, and heat treatment. The use of various modifiers is also described, and a particularly positive effect of membrane modification on the separation selectivity is highlighted. Among various polymers, hydrophilic PVA-based membranes stand out for optimal transport properties that they offer for EG dehydrating. Fabricating of TFC membranes with a microporous support layer appears to be a viable approach to the development of productivity without selectivity loss. Special attention is given to the recovery of methanol from EG, including extensive studies of the separation performance of polymer membranes. Membranes based on a CS/PVP blend with inorganic modifiers are specifically promising for methanol removal. With regard to polymer wettability properties, it is worth mentioning that membranes based on hydrophobic polymers (e.g., SPEEK, PBI/PEI, PEC, PPO) are capable of exhibiting much higher selectivity due to diffusion limitations.

Impact of Layered Perovskite Oxide La0.85Yb0.15AlO3 on Structure and Transport Properties of Polyetherimide.

This study aims to improve properties of Ultem® polyetherimide (PEI) by incorporating up to 2 wt% additives of the perovskite oxide La0.85Yb0.15AlO3 (LYA). The structure of dense PEI/LYA films was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) in combination with an analysis of their elemental composition using energy-dispersive spectroscopy (EDS). The PEI/LYA films exhibit a two-layer structure. Contact angle measurements revealed hydrophilization of the membrane surface enriched with the perovskite. The transport properties were tested via gas separation and pervaporation processes. The separation selectivity of He/N2 and O2/N2 gas pairs increased with the growth of the LYA content in the membranes. Pervaporation of a methanol(MeOH)-cyclohexane(CH) mixture was effective due to the high sorption of MeOH in the PEI/LYA membranes. The maximal pervaporation separation index was found for the PEI/LYA(2%) membrane.

Enhancing Pervaporation Membrane Selectivity by Incorporating Star Macromolecules Modified with Ionic Liquid for Intensification of Lactic Acid Dehydration.

Modification of polymer matrix by hybrid fillers is a promising way to produce membranes with excellent separation efficiency due to variations in membrane structure. High-performance membranes for the pervaporation dehydration were produced by modifying poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) to facilitate lactic acid purification. Ionic liquid (IL), heteroarm star macromolecules (HSM), and their combination (IL:HSM) were employed as additives to the polymer matrix. The composition and structure of hybrid membranes were characterized by X-ray diffraction and FTIR spectroscopy. Scanning electron microscopy was used to investigate the membranes surface and cross-section morphology. It was established that the inclusion of modifiers in the polymer matrix leads to the change of membrane structure. The influence of IL:HSM was also studied via sorption experiments and pervaporation of water‒lactic acid mixtures. Lactic acid is an essential compound in many industries, including food, pharmaceutical, chemical, while the recovering and purifying account for approximately 50% of its production cost. It was found that the membranes selectively remove water from the feed. Quantum mechanical calculations determine the favorable interactions between various membrane components and the liquid mixture. With IL:HSM addition, the separation factor and performance in lactic acid dehydration were improved compared with pure polymer membrane. The best performance was found for (HSM: IL)-PPO/UPM composite membrane, where the permeate flux and the separation factor of about 0.06 kg m-2 h-1 and 749, respectively, were obtained. The research results demonstrated that ionic liquids in combination with star macromolecules for membrane modification could be a promising approach for membrane design.

Development of Novel Polyamide-Imide/DES Composites and Their Application for Pervaporation and Gas Separation.

Novel polymer composites based on polyamide-imide Torlon and deep eutectic solvent (DES) were fabricated and adapted for separation processes. DES composed of zinc chloride and acetamide in a ratio of 1:3 M was first chosen as a Torlon-modifier due to the possibility of creating composites with a uniform filling of the DES through the formation of hydrogen bonds. The structure of the membranes was investigated by scanning electron microscopy and X-ray diffraction analysis; thermal stability was determined by thermogravimetric analysis and mass spectrometry. The surface of the composites was studied by determining the contact angles and calculating the surface tension. The transport properties were investigated by such membrane methods as pervaporation and gas separation. It was found that the inclusion of DES in the polymer matrix leads to a significant change in the structure and surface character of composites. It was also shown that DES plays the role of a plasticizer and increases the separation performance in the separation of liquids and gases. Torlon/DES composites with a small amount of modifier were effective in alcohol dehydration, and were permeable predominantly to water impurities in isopropanol. Torlon/DES-5 demonstrates high selectivity in the gas separation of O2/N2 mixture.

Application of Polymer Membranes for a Purification of Fuel Oxygenated Additive. Methanol/Methyl Tert-butyl Ether (MTBE) Separation via Pervaporation: A Comprehensive Review.

Methyl Tert-butyl Ether (MTBE) remains the most popular fuel additive to improve fuel performance and reduce the emission of hazardous components. The most common method of MTBE production is a catalytic synthesis with a great excess of methanol to improve the reaction yield. The problems of obtaining pure MTBE from the final product have determined the search for new techniques; primarily membrane methods. Pervaporation as an optimal membrane process for highly selective separation of organic mixtures is of particular interest. This review is focused on analysis of the research works on the various polymer membranes and their efficiency for the separation of the azeotropic methanol/MTBE mixture. Currently the most popular materials with optimal transport properties are poly(vinyl alcohol), cellulose acetate and polyheteroarylenes. Mixed matrix membranes (MMM) are highly effective as well as they show overall operational stability.

Strongly Selective Polymer Membranes Modified with Heteroarm Stars for the Ethylene Glycol Dehydration by Pervaporation.

Hybrid membranes based on poly (2,6-dimethyl-1,4-phenylene oxide) modified with heteroarm stars (HAS) were developed to separate ethylene glycol/water mixtures by pervaporation. The HAS consist of a small branching center fullerene C 60 and twelve arms of different nature, six arms of nonpolar polystyrene and six arms of polar poly-tert-butyl methacrylate. The changes of structure and physical properties with HAS inclusion were systematically studied using SEM, X-ray diffraction analysis, TGA, and contact angle measurements. Mass transfer of ethylene glycol and water through membranes was studied by sorption and pervaporation tests. It was found that the growth of HAS content up to 5 wt% in the membrane leads to an increase in the total flux and a strong increase in the separation factor. To evaluate intrinsic properties of the penetrant ‒membrane system, permeability and selectivity were calculated. Overall, utilizing star-shaped macromolecules as a filler can be a promising way to improve the separation performance of diffusion membranes.

Novel Polyester Amide Membranes Containing Biquinoline Units and Complex with Cu(I): Synthesis, Characterization, and Approbation for n-Heptane Isolation from Organic Mixtures.

The wide possibilities of designing a chemical structure and creating complexes with transition metals make polymers of heteroaromatic structure interesting objects, from both scientific and practical aspects. In this work, modern biquinoline-containing polymers, namely polyester amide (PEA) and its metal-polymer complex (PEA-Cu(I)), were synthesized and used to form dense flat membranes. A comparative study of their morphology, same physical properties (density, free volume, and contact angles), and thermomechanical characteristics was carried out. The transport properties of the modern membranes were studied during pervaporation, to solve a problem of n-heptane isolation from its binary mixtures with thiophene and methanol. It was shown that only the PEA membrane is selective for the separation of thiophene impurities from the mixture with n-heptane. In pervaporation of methanol/n-heptane mixture, the РЕА-Cu(I) membrane exhibits significantly higher pervaporation separation index, as compared with that of the РЕА membrane.

Asymmetric Membranes Based on Copolyheteroarylenes with Imide, Biquinoline, and Oxazinone Units: Formation and Characterization.

Modern ultrafiltration requires novel perfect membranes with narrow pore size, high porosity, and minimal pore tortuosity to achieve high separation performance. In this work, copolyamic acid (co-PAA) was synthesized and used for the preparation of asymmetric porous membranes by phase inversion technique. Several co-PAA membranes were heated up to 250 °C; during heating, they undergo solid-phase transformation into co-polybenzoxazinoneimide (co-PBOI) via dehydration and cyclization. Comparative characterization of both co-PAA and co-PBOI membranes was realized by scanning electron microscopy, mechanical testing, thermogravimetric analysis, and ultrafiltration experiments. Membrane calibration was carried out using a mixture of seven proteins with different molecular weights. During heat treatment, the molecular weight cut-off of the membranes decreased from 20 × 103 g/mol (co-PAA) to 3 × 103 g/mol (co-PBOI). Abnormally low dispersions of rejection (0.3 for co-PAA and 0.45 for co-PBOI) were observed for the studied membranes; this fact indicates that the membranes possess enhanced resolving power.

Thermochemical study of gaseous indium-arsenic sulfosalt.

RATIONALE: Sulfide systems are often used at high temperatures, when vaporization of the components is enabled. Sulfide ores are used as sources of various metals and nonmetals and gaseous sulfides, and sulfosalts may also play a role in the atmosphere chemistry of hot rocky exoplanets. To predict the existence and thermal stability of gaseous sulfides and sulfosalts it is important to know their thermodynamic characteristics. In this study the sulfosalt of indium and arsenic was obtained in the gaseous phase for the first time. METHODS: High-temperature Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species over indium and arsenic sulfides. A molybdenum double two-temperature cell was used to create the conditions of coexistence of indium and arsenic sulfides. A theoretical study of gaseous As4 S4 and In2 AsS2 was performed using both B3LYP, M06, PBE0 and TPSSh hybrid DFT functionals and an ab initio wave function-based MP2(Full) method. RESULTS: Gaseous In2 AsS2 has been identified during vaporization of In6 S7 and As2 S3 from the molybdenum double two-temperature cell. The structure and molecular parameters of gaseous In2 AsS2 were determined using quantum chemical calculations. Energetically favorable structures of gaseous In2 S, AsS, As4 S4 and In2 AsS2 were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous In2 AsS2 (186 ± 37 kJ mol-1 ) was derived as a result of measurements of the equilibrium constants of two independent gas-phase reactions. CONCLUSIONS: The gaseous sulfosalt of indium and arsenic was obtained for the first time. The formation enthalpy of the In2 AsS2 (g) molecule at 298 K was evaluated both experimentally and theoretically. The thermal stability of the gaseous sulfosalt is less than that of the gaseous oxyacid salts.

Improved Hydrogen Separation Using Hybrid Membrane Composed of Nanodiamonds and P84 Copolyimide.

Membrane gas separation is a prospective technology for hydrogen separation from various refinery and petrochemical process streams. To improve efficiency of gas separation, a novel hybrid membrane consisting of nanodiamonds and P84 copolyimide is developed. The particularities of the hybrid membrane structure, physicochemical, and gas transport properties were studied by comparison with that of pure P84 membrane. The gas permeability of H2, CO2, and CH4 through the hybrid membrane is lower than through the unmodified membrane, whereas ideal selectivity in separation of H2/CO2, H2/CH4, and CO2/CH4 gas pairs is higher for the hybrid membrane. Correlation analysis of diffusion and solubility coefficients confirms the reliability of the gas permeability results. The position of P84/ND membrane is among the most selective membranes on the Robeson diagram for H2/CH4 gas pair.

Impact of Endometallofullerene on P84 Copolyimide Transport and Thermomechanical Properties.

Novel polymer composite materials, including unique nanoparticles, contribute to the progress of modern technologies. In this work, the endohedral fullerene C60 with incapsulated iron atom (endometallofullerene Fe@C60) is used for modification of P84 copolyimide. The impact of 0.1, 0.5, and 1 wt % endometallofullerene on the structure and physicochemical properties of polymer films is studied through scanning electron microscopy, thermogravimetric analysis, and thermomechanical tests. Transport properties are estimated through sorption and pervaporation techniques toward methanol and methyl acetate mixture. The inclusion of endometallofullerene into the copolyimide matrix improves membrane permeability and selectivity in the separation of methanol-methyl acetate mixtures. The maximal effect is achieved with a composite containing 0.5 wt % Fe@C60. The developed composites are effective for energy and resource saving purification of methyl acetate by pervaporation.