The rheological properties, spinnability, and thermal–oxidative stabilization of high-molecular-weight linear polyacrylonitrile (PAN) homopolymers (molecular weights M_η = 90–500 kg/mol), synthesized via a novel metal-free anionic polymerization method, were investigated to reduce coagulant use, enable solvent recycling, and increase the carbon yield of the resulting carbon fibers. This approach enabled the application of the mechanotropic (non-coagulating) spinning method for homopolymer PAN solutions in a wide range of molecular weights and demonstrated the possibility of achieving a high degree of fiber orientation and reasonable mechanical properties. Rheological analysis revealed a significant increase in solution elasticity (G′) with increasing molecular weight, facilitating the choice of optimal deformation rates for effective chain stretching prior to strain-induced phase separation during the eco-friendly spinning of concentrated solutions without using coagulation baths. The possibility of collecting ~80 wt% of the solvent at the first stage of spinning from the as-spun fibers was shown. Transparent, defect-free fibers with a tensile strength of up to 800 MPa and elongation at break of about 20% were spun. Thermal treatment up to 1500 °C yielded carbon fibers with a carbon residue of ~50 wt%, in contrast to ~35 wt% for industrial radically polymerized PAN carbonized under the same conditions.

The fiber formation process via the uniaxial stretching jet of concentrated polyacrylonitrile solutions in dimethyl sulfoxide has been investigated. Data on viscoelastic properties obtained by oscillatory shear rheometry have been compared with the evolution of jet thinning during stretching. It was found that at a fixed temperature and moderate air humidity (20%), the jet thinning process involves an initial rapid viscous thinning followed by phase separation and the formation of solid fibers coated with solvent droplets. Changes in morphology as the solution transforms into solid fiber were analyzed using cryo-microscopy. It was demonstrated that at the final thinning stages there exists an increase in a solvent concentration in the near-surface layers of the jet/fiber. Finally, the role of air humidity was analyzed. Two possible scenarios of fiber formation were considered: predominantly due to uniaxial deformation or through coagulation of solution with moisture from the air humidity. Comparative morphological analysis of prepared fiber cross sections showed that monolithic fibers with homogeneous transverse morphology are obtained in the case of strain-induced formation. In contrast, fibers obtained due to phase separation induced by air humidity have gradient porosity. The mechanisms underlying the observed behavior are discussed.

This study focuses on the development of environmentally sustainable polypropylene (PP)-based composites with the potential for biodegradability by incorporating cellulose and the oligomeric siloxane ES-40. Targeting industrial applications such as fused deposition modeling (FDM) 3D printing, ES-40 was employed as a precursor for the in situ formation of silica particles via hydrolytic polycondensation (HPC). Two HPC approaches were investigated: a preliminary reaction in a mixture of cellulose, ethanol, and water, and a direct reaction within the molten PP matrix. The composites were thoroughly characterized using rotational rheometry, optical microscopy, differential scanning calorimetry, and dynamic mechanical analysis. Both methods resulted in composites with markedly reduced crystallinity and shrinkage compared to neat PP, with the lowest shrinkage observed in blends prepared directly in the extruder. The inclusion of cellulose not only enhances the environmental profile of these composites but also paves the way for the development of PP materials with improved biodegradability, highlighting the potential of this technique for fabricating more amorphous composites from crystalline or semi-crystalline polymers for enhancing the quality and dimensional stability of FDM-printed materials.

In this study, polymer composites based on a polypropylene (PP) matrix with the addition of cellulose and ES-40, used as a silica precursor, were investigated. These composites were designed to achieve enhanced biodegradability through the incorporation of bioavailable cellulose and to enable subsequent carbonization into carbon–silicon carbide systems. Rheological investigations revealed that the multicomponent mixtures exhibited pseudoplastic behavior over the shear rate range typical of injection molding, ensuring process stability without additional plasticization. Morphological analysis demonstrated that an optimal balance of PP, cellulose, and ES-40 promoted the formation of a three-dimensional network structure, leading to a significant increase in flexural modulus at the equal flexural strength despite some reduction in tensile strength. It was further shown that substituting fibrous cellulose with microcrystalline cellulose improved the composite homogeneity, thereby enhancing the density and mechanical properties, especially in systems with low polymer contents. Preliminary pyrolysis experiments indicated that these injection-molded composites can serve as precursors for fabricating bulk thermally stable products containing silicon carbide particles. The obtained results underscore the high potential of the developed materials for applications in conventional injection molding, the possibility of additive manufacturing, and processes requiring subsequent carbonization.