We present basic experimental data and the theoretical background of a novel technique for fiber spinning from polymer solutions. The principal feature of the advanced process is realization of phase separation with detachment of a solvent, accompanied by the orientation of macromolecules, under the action of high extension rates. This is similar in some respects to dry spinning, though the driving force is not diffusion with subsequent evaporation of a solvent but redistribution of polymer-solvent interactions in favor of polymer-polymer and solvent-solvent ones governed by mechanical stresses. A promise of this approach has been demonstrated by experiments performed with polyacrylonitrile solutions in different solvents and solutions of the rigid-chain aromatic polyamide. We examined mechanotropic fiber spinning in model experiments with stretching jets from a drop of polymer solution in different conditions, and then demonstrated the possibility of realizing this process in the stable long-term continuous mode. During extension, phase separation happens throughout the whole section of a jet, as was confirmed by visual observation. Then a solvent diffuses on a jet surface, forming a liquid shell on the oriented fiber. Instability of this cover due to surface tension leads either to formation of separate solvent drops “seating” on the fiber or to the flow of a solvent down to the Taylor cone. The separate liquid droplets can be easily taken off a fiber. The physics underlying this process is related to the analysis of the influence of macromolecule coil-to-stretched chain transition on the intermolecular interaction.
ABSTRACT:The rheological properties of adhesive miscible blends of high-molecular-weight poly(N-vinyl pyrrolidone) (PVP) with short-chain poly(ethylene glycol) (PEG) under oscillatory and steady-state shear flow have been examined with dynamic mechanical and squeezing-flow analysis. The latter allows the rheological characterization of adhesive blends under conditions modeling adhesive-bond formation as a fixed compressive force is applied to an adhesive film. The most adhesive PVP blend with 36 wt % PEG has been established to flow like a viscoplastic (yield stress) liquid with a power-law index of about 0.12. The study of the apparent yield stress as a function of the PVP-PEG composition, content of sorbed water, molecular weight of PVP, and temperature shows that the occurrence of a yield stress in the blends results most likely from a noncovalent crosslinking of PVP macromolecules through short PEG chains by means of hydrogen bonding of both terminal OH groups of PEG to the complementary functional groups in PVP monomer units. A molecular mechanism of PVP-PEG interaction was established earlier by direct and independent methods.
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