Thermochimica Acta 403 (2003) 55–63 Scanning microcalorimetry at high cooling rate S.A. Adamovsky a , A.A. Minakov b , C. Schick a,∗ a Department of Physics, University of Rostock, Universitaetsplatz 3, 18051 Rostock, Germany b Natural Science Center of General Physics Institute, Vavilov st. 38, 199911 Moscow, Russia Received 20 November 2002; received in revised form 5 March 2003; accepted 17 March 2003 Abstract Heat capacity measurements at fast cooling and heating were realized for linear polyethylene NBS SRM (standard reference material) 1484 sample, ca. 120ng, in the melting-crystallization region. A commercial vacuum sensor, thermal conductivity gauge TCG-3880, Xensor Integrations, was utilized as a cell for a micro-calorimeter suitable for such measurements. The cell consists of a thin-film Si 3 N x membrane with a film-thermopile and a film-heater, which are formed at the membrane center. The current at the heater as well as the signal from the thermopile were monitored in real time during fast scanning of temperature of the central part of the membrane. The measurements were performed in an ambient gas, so that controlled cooling and heating rates up to 5 × 10 3 K/s were achieved. As conditions were not adiabatic, the heat leakage from the sample was calibrated and was taken into account for heat capacity measurements. A simple calibration algorithm was developed for such measurements. Thus, a step towards ultra fast cooling scanning calorimetry was made. © 2003 Elsevier Science B.V. All rights reserved. Keywords: Ultra fast scanning calorimetry; Scanning microcalorimetry; Melting and crystallization 1. Introduction The interest in ultra fast scanning calorimetry is at least due to three reasons. (i) Most of the modern materials are used in non-equilibrium states. To study the actual ther- modynamic state of such materials at room temperature, e.g. of a semicrystalline polymer, requires high heating rates to prevent reorgani- zation during the scan. These non-equilibrium states are generated by rapid cooling during pro- cessing of the material. Therefore, calorimetric experiments at cooling rates comparable to that ∗ Corresponding author. Tel.: +49-381-4986880; Fax: +49-381-4981644. E-mail address: christoph.schick@physik.uni-rostock.de (C. Schick). during injection molding, as an example, are needed to study phase transitions under realis- tic processing conditions. With common DSC apparatuses, like the Perkin-Elmer Instruments Pyris DSC, calorimetric measurements at con- stant cooling rates up to 500 K/min (ca. 10 K/s) can be realized as shown recently by Mathot and co-workers [1]. Even though Mathot gives interesting results, he uses a cooling rate, which is far too slow to mimic realistic cooling condi- tions at injection molding of thin wall products which may reach hundreds or even thousands of kelvin per second [2–4]. (ii) Currently material science focuses on nano-scale systems. It is very difficult to perform calori- metric measurements of nano-gram samples, like thin films, because the heat flow needed to heat the sample at moderate rates is extremely small 0040-6031/03/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0040-6031(03)00182-5