The process of electrospinning polymer solutions depends on many entry parameters, with each having a significant impact on the overall process and where complexity prevents the expression of their interplay. However, under the assumption that most parameters are fixed, it is possible to evaluate the mutual relations between pairs or triples of the chosen parameters. In this case, the experiments were carried out with a copolymer poly(vinylidene-co-hexafluoropropylene) solved in mixed N,N’-dimethylformamide (DMF)/acetone solvent for eight polymer concentrations (8, 10, 12, 15, 18, 21, 24, and 27 wt.%) and five DMF/acetone ratios (1/0, 4/1, 2/1, 1/1, 1/2). Processing of the obtained data (viscosity, mean nanofiber diameter) aimed to determine algebraic expressions relating both to viscosity and a mean nanofiber diameter with polymer concentration, as well as DMF/acetone ratio. Moreover, a master curve relating these parameters with no fitting factors was proposed continuously covering a sufficiently broad range of concentration as well as DMF/acetone ratio. A comparison of algebraic evaluation with the experimental data seems to be very good (the mean deviation for viscosity was about 2%, while, for a mean nanofiber diameter was slightly less than 10%).

The exponential Phan–Tien and Tanner (PTT), Giesekus, Leonov, and modified extended Pom–Pom (mXPP) differential constitutive models are evaluated in two ways: with regard to steady shear characteristics and with regard to large amplitude oscillatory shear characteristics of a solution of poly(ethylene oxide) in dimethyl sulfoxide. Efficiency of the models with nonlinear parameters optimized with respect to steady shear measurements is evaluated by their ability to describe large amplitude oscillatory shear (LAOS) characteristics. The reciprocal problem is also analyzed: The nonlinear parameters are optimized with respect to the LAOS measurements, and the models are confronted with the steady shear characteristics. In this case, optimization is based on the LAOS measurements and equal emphasis is placed on both real and imaginary parts of the stress amplitude. The results show that the chosen models are not adequately able to fit the LAOS characteristics if the optimization of nonlinear parameters is based on steady shear measurements. It follows that the optimization of nonlinear parameters is much more responsible if it is carried out with respect to the LAOS data. In this case, when the optimized parameters are used for a description of steady shear characteristics, efficiency of the individual models as documented differs.

Electrospinning represents the very effective process of producing nanofibrous mats. This process is influenced by a number of mutually and strongly interlaced entry parameters (characteristics of polymer, solvent, process parameters) and their participation in the resulting nanofiber quality. The appearance of nanofibers is a result of the necessary primary experimental parameter setting within an acceptable range. However, finer analysis of nanofiber quality depends on the proper choice of these individual factors. The aim of this contribution is to evaluate one of the key factors—polymer concentration—with respect to the presence or absence of bead formation. This passage can be approximated by rheological oscillatory measurements when a sudden decrease in phase angle indicates this change. It replaces otherwise time- and cost-consuming trial-and-error experiments. This approach was tested using three different materials: solutions of poly(vinylidene fluoride-co-hexafluoropropylene), poly(vinyl butyral), and poly(ethylene oxide).