The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on strict symmetry of the
twin calorimeter. This symmetry is of particular importance for temperature-modulated DSC (TMDSC) since positive and negative
deviations from symmetry cannot be distinguished in the most popular analysis methods. The heat capacities for sapphire-filled
and empty aluminum calorimeters (pans) under designed cell imbalance caused by different pan-masses were measured. In addition,
the positive and negative signs of asymmetry have been explored by analyzing the phase-shift between temperature and heat
flow for sapphire and empty runs. The phase shifts change by more than 180° depending on the sign of the asymmetry. Once the
sign of asymmetry is determined, the asymmetry correction for temperature-modulated DSC can be made.
Authors:K. Ishikiriyama, A. Boller, and B. Wunderlich
The melting and crystallization of a sharply melting standard has been explored for the calibration of temperature-modulated
differential scanning calorimetry, TMDSC. Modulated temperature and heat flow have been followed during melting and crystallization
of indium. It is observed that indium does not supercool as long as crystal nuclei remain in the sample when analyzing quasi-isothermally
with a small modulation amplitude. For standard differential scanning calorimetry, DSC, the melting and crystallization temperatures
of indium are sufficiently different not to permit its use for calibration on cooling, unless special analysis modes are applied.
For TMDSC with an underlying heating rate of 0.2 K min−1 and a modulation amplitude of 0.5–1.5 K at periods of 30–90 s, the extrapolated onsets of melting and freezing were within
0.1 K of the known melting temperature of indium. Further work is needed to separate the effects originating from loss of
steady state between sample and sensor on the one hand and from supercooling on the other.
Authors:A. Boller, I. Okazaki, K. Ishikiriyama, G. Zhang, and B. Wunderlich
The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on the symmetry of the twin
calorimeters. This symmetry is of particular importance for the temperature-modulated DSC (TMDSC) since positive and negative
deviations from symmetry cannot be distinguished in the most popular analysis methods. Three different DSC instruments capable
of modulation have been calibrated for asymmetry using standard non-modulated measurements and a simple method is described
that avoids potentially large errors when using the reversing heat capacity as the measured quantity. It consists of overcompensating
the temperature-dependent asymmetry by increasing the mass of the sample pan.
Authors:K. Ishikiriyama, M. Todoki, K. H. Min, S. Yonemori, and M. Noshiro
The pore size distributions (PSDs) of microporous glass, which were controlled by acid leaching subsequent to phase separation of CaO-Al2O3-B2O3-SiO2 glass, were determined via both mercury porosimetry and thermoporosimetry (thermal porosimetry). As a result, the pore radii, the cumulative pore volumes, and the surface areas determined via thermoporosimetry were in good agreement with those determined via mercury porosimetry. It was revealed that thermoporosimetry could be applied to pore structure analysis for porous materials having pore sizes at least up to 58 nm in radius.