Ultrafast thermal processing and nanocalorimetry at heating and cooling rates up to 1MK∕s

Abstract

To generate artificial materials with advanced physical and chemical properties and to study phase transition kinetics on submillisecond time scale, an ultrafast nonadiabatic membrane nanocalorimeter was constructed. A set of commercially available membrane gauges for ultrafast nanocalorimetry has been developed. The gauges placed in a thermostat with controlled helium gas pressure and temperature can be utilized as devices for thermal processing and calorimetry with resolution of 1 nJ/K. Controlled ultrafast cooling, as well as heating, up to 10(6) K/s can be attained for nanogram samples. The maximum cooling rate is inversely proportional to the radius of the heated region of the gauge, which was in the range of 10-100 microm depending on the gauge. The minimum addenda heat capacity was 3 nJ/K. The dynamic heat-transfer problem for the temperature distribution in the membrane-gas system at ultrafast processing has been solved. The characteristic rate R(0) corresponding to quasistatic limit of the temperature change in the membrane-gas system has been found to be equal to 10(5) K/s for a 1 microm thick silicon nitride membrane in helium gas. Calorimeter performance at ultrafast rates has been verified by a set of test experiments. The method was applied for thermal processing and calorimetric measurements in a set of linear polymers. It has been established that nearly amorphous polyethylene can be obtained at a cooling rate of 10(6) K/s.