Polyelectrolyte solutions of Nylon 6 in 99 vol% formic acid were electrospun, and the effect of polymer concentration was studied. Using a laser device to locally heat the needle spinneret, the solution temperature was feasibly elevated up to 66 degrees C, and its effect on electrospinning was investigated as well. The microstructure of the as-spun products was characterized by several analytical techniques, including electron diffraction, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction. Based on the solution rheology, the entanglement concentration (c(e)) was determined to be 1 wt%. To prepare bead-free fibers, the minimum polymer concentration was 8 c(e), which was much higher than that (1.75-2.0 c(e)) required for conventional neutral solutions. Increasing the polymer concentration and/or solution temperature led to a gradual change of electrospun products from round fibers with major gamma form crystals to ribbon-like fibers in possession of exclusive alpha form ones. For intermediate concentrations, nanowebs made of nanofibrils with diameters of 20-40 nm were seen. Thin ribbon-like fibers (ca. 40 nm thick) with nanowebs became the dominant products obtained from the 15 wt% solutions at high temperatures. The dramatic variations in morphological features and crystal modification could be thoroughly explained on the basis of the interplay between solvent evaporation at the jet surface and solvent diffusion in the liquid jet. DSC heating traces on the ribbon-like fibers exhibited an unusually high melting temperature of similar to 235 degrees C, which is higher than the equilibrium melting temperature of Nylon 6 crystals of 232 degrees C. (C) 2011 Elsevier Ltd. All rights reserved.