Temperature modulated DSC (TMDSC) -: Applications and limits of phase information, cp determination and effect separation

The ADSC (Alternating DSC [1]) technique superimposes upon the conventional constant heating rate a periodically varying modulation [2-8]. The modulation creates high instantaneous heating rates which increases sensitivity. The low underlying constant heating rate is used to get better resolution. With ADSC it is possible to separate overlapping thermal effects without loss of sensitivity and to determine heat capacities under quasi-isothermal conditions. It has been reported that there are also some limitations for the use of the modulation techniques, i.e. that the accuracy of c(p) determination is reduced at higher modulation frequencies due also to thermal diffusivity within the sample itself [9, 10]. In this contribution, the limitations given by the measuring system itself will be discussed. A key value is the limit frequency of the sensor arrangement. In the Mettler Toledo DSC821 degrees this frequency is approximately 1/3 Hz. From these findings the following recommendations amongst others can be given: for light mass crucibles, 30 s periods are reasonable with amplitudes not exceeding the heating/cooling rates possible. A blank and a calibration measurement will eliminate cell asymmetry and will enhance the accuracy of c(p) measurements even at higher modulation frequencies.