Direct Detection of Effective Glass Transitions in Miscible Polymer Blends by Temperature-Modulated Differential Scanning Calorimetry

2005 ◽  
Vol 38 (6) ◽  
pp. 2355-2361 ◽  
Author(s):  
Yohei Miwa ◽  
Kaori Usami ◽  
Katsuhiro Yamamoto ◽  
Masato Sakaguchi ◽  
Masahiro Sakai ◽  
...  
Keyword(s):  
Differential Scanning Calorimetry ◽  
Polymer Blends ◽  
Direct Detection ◽  
Glass Transitions ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
Miscible Polymer Blends

Quasi-isothermal temperature-modulated differential scanning calorimetry (TMDSC) for the separation of reversible and irreversible thermodynamic changes in glass transition and melting ranges of flexible macromolecules

2009 ◽  
Vol 81 (10) ◽  
pp. 1931-1952 ◽  
Author(s):  
Bernhard Wunderlich
Keyword(s):  
Differential Scanning Calorimetry ◽  
Heat Capacity ◽  
Thermal Analyses ◽  
Data Bank ◽  
Irreversible Thermodynamic ◽  
Modulated Dsc ◽  
Glass Transitions ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
Heat Capacity Measurements

With standard differential scanning calorimetry (DSC), it is possible to derive calorimetric data for equilibrium or metastable samples. The introduction of temperature-modulated DSC (TMDSC) permits in its quasi-isothermal (non-scanning) mode (TMDC), long-time apparent heat capacity measurements of high precision (±1 %). For flexible molecules, heat capacity measurements from the various calorimetric methods could be combined in the ATHAS Data Bank, which now contains experimental data for over 200 materials. These data were linked to the vibrational and large-amplitude motion of the constituent atoms and molecules, to provide a base for the judgement of the thermal analyses, extending outside the range of equilibrium or metastability with an error of only 2-5 %. The TMDC together with DSC is now able to quantitatively assess the reversibility of thermal processes. A sufficient number of systems have been analyzed in this fashion to develop better understanding of macro-, micro-, and nanophases of flexible macromolecules. The new concepts discussed are: (1) multiple glass transitions due to possible rigid-amorphous fractions (RAFs) and glass transitions within crystals, both observed in semicrystalline macromolecules, and (2) locally reversibly melting on the surface of chain-folded crystals. The locally reversible melting decreases with crystal perfection and also disappears when the chains become rigid.

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