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Differential scanning calorimetry (DSC) of semicrystalline polymers

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Abstract

Differential scanning calorimetry (DSC) is an effective analytical tool to characterize the physical properties of a polymer. DSC enables determination of melting, crystallization, and mesomorphic transition temperatures, and the corresponding enthalpy and entropy changes, and characterization of glass transition and other effects that show either changes in heat capacity or a latent heat. Calorimetry takes a special place among other methods. In addition to its simplicity and universality, the energy characteristics (heat capacity C P and its integral over temperature T—enthalpy H), measured via calorimetry, have a clear physical meaning even though sometimes interpretation may be difficult. With introduction of differential scanning calorimeters (DSC) in the early 1960s calorimetry became a standard tool in polymer science. The advantage of DSC compared with other calorimetric techniques lies in the broad dynamic range regarding heating and cooling rates, including isothermal and temperature-modulated operation. Today 12 orders of magnitude in scanning rate can be covered by combining different types of DSCs. Rates as low as 1 μK s−1 are possible and at the other extreme heating and cooling at 1 MK s−1 and higher is possible. The broad dynamic range is especially of interest for semicrystalline polymers because they are commonly far from equilibrium and phase transitions are strongly time (rate) dependent. Nevertheless, there are still several unsolved problems regarding calorimetry of polymers. I try to address a few of these, for example determination of baseline heat capacity, which is related to the problem of crystallinity determination by DSC, or the occurrence of multiple melting peaks. Possible solutions by using advanced calorimetric techniques, for example fast scanning and high frequency AC (temperature-modulated) calorimetry are discussed.

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Notes

  1. One should be always be aware that a temperature near to the sample is measured and not sample temperature itself.

  2. At infinite time heat flow rate from the sample equals zero but, because of asymmetries of the instrument, a non-zero value is measured.

  3. Unfortunately, this is possible only close to glass transition but in most cases not close to melting and crystallization transitions.

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Acknowledgments

I acknowledge the valuable contributions of all my coworkers, especially A. Minakov, M. Merzlyakov, A. Wurm, H. Huth, S. Adamovsky, and E. Zhuravlev, and financial support from the German Science Foundation (DFG) and the European Union which made this paper possible.

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  1. Institute of Physics, University of Rostock, Wismarsche Str. 43-45, 18051, Rostock, Germany

    C. Schick

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Schick, C. Differential scanning calorimetry (DSC) of semicrystalline polymers. Anal Bioanal Chem 395, 1589–1611 (2009). https://doi.org/10.1007/s00216-009-3169-y

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