A new interpretation of the mechanism of the polyvinylidene fluoride (PVDF) membrane formation using the nonsolvent-induced phase separation (NIPS) method based on an analysis of the complete experimental phase diagram for the three-component mixture PVDF–dimethyl acetamide (DMAc)–water is proposed. The effects of the precipitation bath’s harshness and thermodynamic affinity of the polymer’s solvent on the morphology, crystalline structure, transport and physical–mechanical properties of the membranes are investigated. These characteristics were studied via scanning electron microscopy, wide-angle X-ray scattering, liquid–liquid porosimetry and standard methods of physico-mechanical analysis. It is established that an increase in DMAc concentration in the precipitation bath results in the growth of mean pore size from ~60 to ~150 nm and an increase in permeance from ~2.8 to ~8 L m⁻² h⁻¹ bar⁻¹. It was observed that pore size transformations are accompanied by changes in the tensile strength of membranes from ~9 to ~11 and to 6 MPa, which were explained by the degeneration of finger-like pores and appearance of spherulitic structures in the samples. The addition of water to the dope solution decreased both the transport (mean pore size changed from ~55 to ~25 nm and permeance reduced from ~2.8 to ~0.5 L m⁻² h⁻¹ bar⁻¹) and mechanical properties of the membranes (tensile strength decreased from ~9 to ~6 MPa). It is possible to conclude that the best membrane quality may be reached using pure DMAc as a solvent and a precipitation bath containing 10–30% wt. of DMAc, in addition to water.

One of the materials that attracts attention as a potential material for membrane formation is ultrahigh molecular weight polyethylene (UHMWPE). One potential material for membrane formation is ultrahigh molecular weight polyethylene (UHMWPE). The present review summarizes the results of studies carried out over the last 30 years in the field of preparation, modification and structure and property control of membranes made from ultrahigh molecular weight polyethylene. The review also presents a classification of the methods of membrane formation from this polymer and analyzes the conventional (based on the analysis of incomplete phase diagrams) and alternative (based on the analysis of phase diagrams supplemented by a boundary line reflecting the polymer swelling degree dependence on temperature) physicochemical concepts of the thermally induced phase separation (TIPS) method used to prepare UHMWPE membranes. It also considers the main ways to control the structure and properties of UHMWPE membranes obtained by TIPS and the original variations of this method. This review discusses the current challenges in UHMWPE membrane formation, such as the preparation of a homogeneous solution and membrane shrinkage. Finally, the article speculates about the modification and application of UHMWPE membranes and further development prospects. Thus, this paper summarizes the achievements in all aspects of UHMWPE membrane studies.

A concept according to which semicrystalline polymers, in terms of their phase state, are treated as specific (metastable and microheterogeneous) liquids is proposed. Literature evidence and experimental data obtained by the authors serve as the basis for the discussion of structural and thermodynamic features of these liquids, which manifest themselves during contact with low-molecular-mass compounds.

For the first time, the presence of acetone in the casting solutions of polyacrylonitrile (PAN) in dimethylsulfoxide or N-methyl-2-pyrrolidone was studied with regards to thermodynamical aspects of phase separation of polymeric solutions induced by contact with non-solvent (water), formation and performance of porous membranes of ultrafiltration range. The positions of the liquid equilibrium binodals on the phase diagrams of these three-component and pseudo-three-component mixtures were determined. For PAN—N-methyl-2-pyrrolidone—water glass transition curve on a ternary phase diagram was plotted experimentally for the first time. The real-time evolution of the structure of mixtures of PAN with solvents (co-solvents) upon contact with a non-solvent (water) has been studied. The thermodynamic analysis of the phase diagrams of these mixtures, together with optical data, made it possible to propose a mechanism of structure formation during non-solvent induced phase separation of different mixtures. The addition of acetone promotes the formation of a spongy layer on the membrane surface, which decreases the probability of defect formation on the membrane surface and keeps finger-like macrovoids from the underlying layers of the membrane. It was shown that the molecular weight cut-off (MWCO) of the membranes can be improved from 58 down to 1.8 kg/mol by changing the acetone content, while polymer concentration remained the same.