Membrane gas separation using polymeric membranes is one of rapidly developing energy-conserving technologies. This review describes the scope of membrane gas separation problems and demonstrates the relevance of membrane methods for their solution. The basic concepts and regularities of diffusion gas transfer and principles and characteristics of membrane gas separation are considered. The main physicochemical approaches to the selection of membrane materials considering both the properties of the gas–polymer system and the structure and physical properties of polymers are discussed. The considered issues are combined within a common approach to substantiate the choice of both existing commercial polymers and advanced polymeric materials to address important gas separation problems such as separation of air components; carbon dioxide, hydrogen and helium recovery from natural and industrial gas mixtures; and separation of a nitrogen and methane mixture. The avenues of development of the membrane materials science to solve each of the mentioned problems of membrane gas separation are demonstrated. The review is intended for specialists in the synthesis and physics of polymers for planning the research and assessing the applicability of polymeric materials for various practical gas separation problems and for specialists in the membrane materials science and membrane technology. The bibliography includes 165 references.

A direct fluorination technique was applied for the surface treatment of PIM-1 films in a liquid phase (perfluorodecalin). The fluorinated samples were analyzed by various instrumental techniques. ATR-IR spectroscopy showed that the fluorination predominantly takes place in methylene- and methyl-groups. Cyano-groups, aromatic hydrogens and the aromatic structure of the PIM-1 repeat unit were shown to be relatively stable at the fluorination conditions. XPS confirmed that the concentration of fluorine, as well as oxygen, in the near surface layer (~1 nm) increases with fluorination time. C1s and O1s surface spectra of the fluorinated PIM-1 samples indicated an appearance of newly-formed C-F and C-O functional groups. Scanning electron microscopy and X-ray energy-dispersive spectroscopy of the fluorinated PIM-1 samples showed an increase of the fluorine concentration at the surface (~0.1–1 μm) with the treatment duration. Analysis of the slices of the PIM-1 films demonstrated a decline of the fluorine content within several microns of the film depth. The decline increased with the fluorination time. A model of fluorine concentration dependence on the film depth and treatment duration was suggested. A change in the specific free surface energy as a result of PIM-1 fluorination was revealed. The fluorination time was shown to affect the surface energy (γ_SV), providing its shift from a low value (25 mJ∙m⁻²), corresponding to tetrafluoroethylene, up to a relatively high value, corresponding to a hydrophilic surface.

Previously, we found that modification of the membrane surface from polyvinyltrimethylsilane (PVTMS) by treatment with low-temperature plasma induced by low pressure DC discharge leads to a significant increase in gas separation characteristics. To understand the mechanism of this phenomenon, in this article XPS combined with precision etching 10 keV beam of Ar₂₅₀₀⁺ clusters was used for depth profiling of PVTMS spin-coated films before and after DC discharge treatment. The etching craters depths were measured by stylus surface profiler. The average etching rate of the untreated PVTMS film by Ar₂₅₀₀⁺ clusters was defined (230 nm/min). It was found that the low temperature plasma treatment of PVTMS leads to a sharp increase in the oxygen concentration on a surface with a simultaneous decrease in the carbon content. The experimental data obtained indicate also that the treatment of PVTMS film by plasma leads not only to a change in the chemical structure of the surface, but also to the formation of a gradient subsurface layer with a thickness of about 50 nm.

Poly(vinyl trimethylsilane) (PVTMS) films were subjected to direct surface fluorination in liquid medium (perfluorodecalin). The samples were investigated using several techniques: SEM-XEDS, XPS, ATR-IR, and contact angle measurement. The methods used allowed us to estimate chemical changes occurring because of the treatment. ATR-IR showed that most of the changes occurred in the Si(CH₃)₃ group. Monofluorinated Si(CH₃)₃ groups formed in the near-surface layer (Ge crystal, 0.66 µm penetration) after 30 min of fluorination, and then di- and trifluorinated groups appeared. Oxidation of the film with oxygen was also shown with the use of ZnSe crystal (2 µm penetration). The XPS method allowed an assessment of the ratio of the main elements at the surface of the fluorinated film. Two different exponential models were proposed to fit the experimental data of SEM-XEDS. Based on the model with the intercept, the depth of fluorination was estimated to be ≤1.1 µm, which is consistent with the result from the literature for the gas-phase fluorination. Contact angle measurements showed that oxidation of the PVTMS surface prevailed for the first 45 min of fluorination (surface hydrophilization) with a subsequent fluorine content increase and hydrophobization of the surface upon 60 min of fluorination.

New hollow fiber gas separation membranes with a non-porous selective layer based on poly(4-methyl-1-pentene) (PMP) granules have been obtained using the solution-free melt spinning process. The influence of the preparation conditions on the geometry of the obtained samples was studied. It was found that a spin head temperature of 280 °C and a specific mass throughput of 103 g mm⁻² h⁻¹ are optimal to obtain defect-free, thin-walled hollow fibers in a stable melt spinning process, using the given spinneret geometry and a winding speed of 25 m/min. The gas permeability and separation properties of new fibers were studied using CO₂/N₂ and CO₂/CH₄ mixtures, and it was found that the level of gas selectivity characteristic of homogeneous polymer films can be achieved. The features of the gas mixture components permeability below and above the PMP glass transition temperature have been experimentally studied in the range of CO₂ concentrations from 10 to 90% vol. The temperature dependences of the permeability of the CO₂/CH₄/N₂ mixture through the obtained HF based on PMP have been investigated, and the values of the apparent activation energies of the permeability have been calculated, which make it possible to predict the properties of membrane modules based on the obtained membranes in a wide temperature range.