Strength of structural materials and fibers is usually increased at the expense of strain at failure and toughness. Recent experimental studies have demonstrated improvements in modulus and strength of electrospun polymer nanofibers with reduction of their diameter. Nanofiber toughness has not been analyzed; however, from the classical materials property trade-off, one can expect it to decrease. Here, on the basis of a comprehensive analysis of long (5–10 mm) individual polyacrylonitrile nanofibers, we show that nanofiber toughness also dramatically improves.
Reduction of fiber diameter from 2.8 μm to 100 nm resulted in simultaneous increases in elastic modulus from 0.36 to 48 GPa, true strength from 15 to 1750 MPa, and toughness from 0.25 to 605 MPa with the largest increases recorded for the ultrafine nanofibers smaller than 250 nm. The observed size effects showed no sign of saturation. Structural investigations and comparisons with mechanical behavior of annealed nanofibers allowed us to attribute ultrahigh ductility (average failure strain stayed over 50%) and toughness to low nanofiber crystallinity resulting from rapid solidification of ultrafine electrospun jets. Demonstrated superior mechanical performance coupled with the unique macro-nano nature of continuous nanofibers makes them readily available for macroscopic materials and composites that can be used in safety-critical applications. The proposed mechanism of simultaneously high strength, modulus, and toughness challenges the prevailing 50 year old paradigm of high-performance polymer fiber development calling for high polymer crystallinity and may have broad implications in fiber science and technology.