Mapping the Influence of Solvent Composition over the Characteristics of Polylactic Acid Nanofibers Fabricated by Electrospinning

Abstract This study investigated the solubility of poly(lactic acid) (PLA) in various solvents (to achieve an 8 % (w/v) polymer solution) and its impact on the morphology of electrospun PLA nanofibers. Several solvents, such as dichloromethane (DCM), chloroform (CHL), tetrahydrofuran (THF), acetone (AC), acetonitrile (ACTNR), dimethylformamide (DMF), dimethylacetamide (DMAc), ethylene glycol (ETGLY), distilled water (WATER), methanol (MEOH), formic acid (FA), and n‐hexane (NHX) were used in their pure and binary forms at several ratios (4 : 1, 2 : 1, 1 : 1, 1 : 2, 1 : 3, and 1 : 4). The study aims to explore the correlation between PLA solubility and its electrospinnability using solvents mapped from the Teas graph across different parameter zones and chemical groups. Hansen solubility parameters, including dispersion cohesion fractional solubility parameter (fd), the polar cohesion fractional solubility parameter (fp) was employed to identify the most effective solvents for PLA dissolution. Teas graph analysis highlighted a correlation between PLA solubility and solvent proximity to Hansen solubility parameters. Additionally, the solubility time varied between 1 hour and 24 hours. Polar solvents such as DCM, CHL, THF, ACTNR, and FA were able to dissolve 8 % (w/v) of PLA at different times, but only very high and effective dissolution of PLA was achieved in pure DCM and CHL whereas FA dissolved PLA in 24 hours, which resulted in the slowest solubility rate. Several structures of nanofibers, such as smooth, heterogenous, porous, fibrous, and beaded, were observed and discussed accordingly in terms of solvent type and ratio. The average nanofiber diameter ranged between 0.18 μm and 3.81 μm. Moreover, physical tests, including surface tension, density, viscosity, and conductivity, were conducted on solvent systems and CHL displayed higher viscosity, while ACTNR had the lowest viscosity and highest conductivity among pure solvents. According to the results of our study, it is possible to design further studies with the aim of deciding which solvents or binary forms should be applied to dissolve PLA within a certain time. The desired structure can be easily arranged to be used as a filter, biomimicking tissue environment, drug delivery system, or extra.