The dissolution advantage of amorphous solids can be negated either by crystallization of the amorphous solid on contact with the dissolution medium or through rapid crystallization of the supersaturated solution. Polymeric additives can potentially retard both of these crystallization routes, leading to the generation of supersaturated solutions that can persist for biologically relevant timeframes.

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Uniform nylon 6 nanofibers with diameters around 200 nm were prepared by electrospinning. Polymorphic phase transitions and crystal orientation of nylon 6 in unconfined (i.e., as-electrospun) and a high T g (340 °C) polyimide confined nanofibers were studied. Similar to melt-spun nylon 6 fibers, electrospun nylon 6 nanofibers also exhibited predominant, meta-stable γ crystalline form, and the γ-crystal (chain) axes preferentially oriented parallel to the fiber axis. Upon annealing above 150 °C, γ-form crystals gradually melted and recrystallized into the thermodynamically stable α-form crystals, which ultimately melted at 220 °C. Release of surface tension accompanied this meltrecrystallization process, as revealed by differential scanning calorimetry. For confined nanofibers, both the melt-recrystallization and surface tension release processes were substantially depressed; γ-form crystals did not melt and recrystallize into α-form crystals until 210 °C, only 10 °C below the T m at 220 °C. After complete melting of nano-confined crystals at 240 °C and recrystallization at 100 °C, only α-form crystals oriented perpendicular to the nanofiber axis were obtained. In the polyimide-confined nanofibers, the Brill transition (from the monoclinic α-form to a high temperature monoclinic form) was observed at 180-190 °C, which was at least 20 °C higher than that in unconfined nylon 6 at approximately 160 °C. This, again, was attributed to the confinement effect.