What Thermal Analysis Can Tell Us About Melting of Semicrystalline Polymers: Exploring the General Validity of the Technique.

Thermal characterization of semicrystalline polymers can constitute a difficult task due to the metastable nature of polymer crystals. It is well documented that polymer structure can reorganize during the thermoanalytical experiment. It has become also clear that thermal analysis alone cannot discriminate the reorganization processes from multiple melting events. Therefore, instead of studying the initial sample state the measurements may simply reflect the structural evolution uncontrollably occurring during the experiment. Here an original setup combining in situ ultrafast chip calorimetry with millisecond time-resolved X-ray scattering is used to find the structural signature of the reorganization processes. The information is further used to construct the heating-rate versus crystallization-temperature reorganization (HR-CT-R) diagram. The diagram allows rationally designing thermoanalytical experiments in which one can completely exclude uncontrolled evolution of the semicrystalline structure. For a typical aromatic polyester, poly(trimethylene terephthalate), the critical heating rate above which all reorganization processes cease to exist can reach 1000 K/s and more.