Optical birefringence and molecular orientation of electrospun polycaprolactone fibers by polarizing-interference microscopy

The potential of polarizing-interference Pluta microscope for determination of optical birefringence of individual nanofibers formed by electrospinning was shown. This technique can be applied for measurements of fiber birefringence, practically at diameter above 300 nm. The molecular orientation of individual polycaprolactone (PCL) nanofibers was determined from birefringence assuming the same orientation of both phases, crystal and amorphous. The molecular orientation was determined using DSC crystallinity, crystal intrinsic birefringence calculated for the first time for PCL from bond polarizabilities as well as estimated value of amorphous intrinsic birefringence. Our results indicate that the birefringence and thus molecular orientation are strongly inhomogeneous along the nanofibers, reflecting a complex nature of forces acting during electrospinning process. The average molecular orientation is weak if any, being dependent together with fiber thickness and crystallinity on electrospinning parameters, like applied voltage, concentration and type of solvent. The obtained results indicate that the average molecular orientation displays similar dependence on applied voltage as fiber diameter. Relatively low melting temperature of electrospun nanofibers suggests low crystal size and/or high concentration of defects in crystals. This observation corresponds with low crystallinity and molecular orientation, indicating together relatively low degree of crystal ordering due to high rate of cooling and solvent evaporation during electrospinning, limiting thus crystallization process.