1. Refers to a change of state induced by changing temperature or pressure (or volume) from one thermodynamic equilibrium to another Refers to the time required to respond to the time required to respond To a change in temperature or pressure (or volume). It also implies Some measure of the molecular motion, especially near a transition Condition. Frequently, an external stress is present permitting the re- Laxation to be measured Refers to the emission or absorption of energy – that is a loss peak – at a transition

4. heat flux or c p poly(dimethyl siloxane) (PDMS) glass transition enthalpy relaxation cold crystallization melting

6. T t T(t) slope: C p can be calculated from the heat flux  Q  Q  is determined by the exactness of the signal M*is determined by the exactness of the program rates

7. Consequently, a correction is needed that is independent of the parameters of the instrument: M. J. O`Neill, Anal. Chem. 38 (1966) 1331 T g, T m, T cr, T S-N, T SA-SC,…T N-I …

8. Classification of the thermodynamic transitions according to Paul Ehrenfest *) : Discontinuity the derivative (1 st, 2 nd,…) of the Gibbs function G *) Ehrenfest P Proc Kon Akad Wetensch Amsterdam (1933) 36, 153

11. First Order Transitions

12. In a real experiment heat transfer requires time and a temperature gradient and this is what we actually see: a (endothermal) melting peak 

13. thermodynamic equilibrium melting temperature experimental melting temperature isothermal crystallization temperature stability parameter slope J. D. Hoffman, J. J. Weeks, J. Res. Bureau Standards 66A (1962) 13 *(solution crystl.) Hoffman & Weeks Plot*

14. Volume Enthalpy Storage modulus At the glass transition Expansivity Heat capacity Loss modulus

15. T V spec H spec (dV/dT)~  (dH/dT) p = c p T cr Tg 1 Tg 2 high cooling rate CR1 low cooling rate CR2 T i2 Tg 2 T e2 Tg 1

16. Calculation of Tg according to M. J. Richardson, N. G. Savill, Brit. Polym. J. 11 (1979) 123 Tg determined independent of the heating rate

17. integration

24. time