Whilst the physics of both classical evaporation and supercritical fluid mixing are reasonably well characterized and understood in isolation, little is known about the transition from one to the other in the context of liquid fuel systems. The lack of experimental data for microscopic droplets at realistic operating conditions impedes the development of phenomenological and numerical models. To address this issue we performed systematic measurements using high-speed long-distance microscopy, for three single-component fuels (n-heptane, n-dodecane, n-hexadecane), into gas at elevated temperatures (700-1200 K) and pressures (2-11 MPa). We describe these high-speed visualizations and the time evolution of the transition from liquid droplet to fuel vapour at the microscopic level. The measurements show that the classical atomization and vaporisation processes do shift to one where surface tension forces diminish with increasing pressure and temperature, but the transition to diffusive mixing does not occur instantaneously when the fuel enters the chamber. Rather, subcritical liquid structures exhibit surface tension in the near-nozzle region and then, after time surrounded by the hot ambient gas and fuel vapour, undergo a transition to a dense miscible fluid. Although there was clear evidence of surface tension and primary atomization for n-dodecane and n-hexadecane for a period of time at all the above conditions, n-heptane appeared to produce a supercritical fluid from the nozzle outlet when injected at the most elevated conditions (1200 K, 10 MPa). This demonstrates that the time taken by a droplet to transition to diffusive mixing depends on the pressure and temperature of the gas surrounding the droplet as well as the fuel properties. We summarise our observations into a phenomenological model which describes the morphological evolution and transition of microscopic droplets from classical evaporation through a transitional mixing regime and towards diffusive mixing, as a function of operating conditions. We provide criteria for these regime transitions as reduced pressure-temperature correlations, revealing the conditions where transcritical mixing is important to diesel fuel spray mixing. (C) 2017 The Authors. Published by Elsevier Ltd.