The aim of the present work was to investigate how the molecular weight (MW) of poly(ethylene oxide) (PEO), a synthetic polymer able to improve alginate (ALG) electrospinnability, could affect ALG-based fiber morphology and mechanical properties. Two PEO grades, having different MWs (high, h-PEO, and low, l-PEO) were blended with ALG: the concentrations of both PEOs in each mixture were defined so that each h-PEO/l-PEO combination would show the same viscosity at high shear rate. Seven ALG/h-PEO/l-PEO mixtures were prepared and characterized in terms of viscoelasticity and conductivity and, for each mixture, a complex parameter rH/rL was calculated to better identify which of the two PEO grades prevails over the other in terms of exceeding the critical entanglement concentration. Thereafter, each mixture was electrospun by varying the process parameters; the fiber morphology and mechanical properties were evaluated. Finally, viscoelastic measurements were performed to verify the formation of intermolecular hydrogen bonds between the two PEO grades and ALG. rH/rL has been proved to be the parameter that better explains the effect of the electrospinning conditions on fiber dimension. The addition of a small amount of h-PEO to l-PEO was responsible for a significant increase in fiber mechanical resistance, without affecting the nano-scale fiber size. Moreover, the mixing of h-PEO and l-PEO improved the interaction with ALG, resulting in an increase in chain entanglement degree that is functional in the electrospinning process.
Keywords: ALG-containing fibers; critical entanglement concentration; electrospinning; intermolecular hydrogen bonds; mechanical properties; molecular weight; poly(ethylene oxide).