Ehrenfestclassification.ppt

3. THE GLASS STATE AND THE GLASS TRANSITION: THERMODYNAMIC and KINETIC ASPECTS Differential Scanning Calorimetry Differential Thermal Analysis Is the glass transition a true thermodynamic phase transition ? ? Tg depends on the cooling rate ? Tg depends on the thermal history sub-Tg aging and annealing Tanneal . Phase transitions of 1st and 2nd order (Ehrenfest classification) Clausius-Clapeyron Ehrenfest Phase transitions of 1st and 2nd order (Ehrenfest classification) 1st-order, 2nd-order and Lambda-type transitions v1 ? v2 s1 ? s2 cp, ?, ?T ? ? v1 = v2 s1 = s2 cp, ?, ?T ? ? v1 = v2 s1 = s2 cp1 ? cp2 ?1 ? ?2 ?T1 ? ?T2 [ T1 = T2 ; P1 = P2 ; g1 = g2 ] Ehrenfest relations Prigogine-Defay ratio must be = 1 if it were a phase transition with a single order parameter using Differential Scanning Calorimetry (DSC, TMDSC…) [J. M. Hutchinson, Thermochimica Acta 324 (1998) 165-174 using Differential Scanning Calorimetry the fictive temperature Tf B2O3 [M. A. R. et al., J. Non-Cryst. Solids 221 (1997) 170] the fictive temperature Tf Ethanol [B. Kabtoul and M. A. R., Phys. Status Solidi A 208, 2249–2253 (2011)] the fictive temperature Tf ? phenomenological Tool-Narayanaswamy-Moynihan (TNM) approach [ Tool, J. Am. Ceram. Soc. 29 (1946) 240. Narayanaswamy, J. Am. Ceram. Soc. 54 (1971) 491. Moynihan et al., J. Am. Ceram. Soc. 59 (1976) 12. ] curve fitting method: [I. M. Hodge, J. Non-Cryst. Solids 169 (1994) 211] THE KAUZMANN PARADOX EXCESS OF ENTROPY: TK W. Kauzmann, Chem. Rev. 43, 219 (1948) THE KAUZMANN PARADOXNN 1.0 STRONG AND FRAGILE GLASS-FORMING LIQUIDS 0 1 Vogel-Tamman-Fulcher equation: (D: strength) fragility index m: STRONG AND FRAGILE GLASS-FORMING LIQUIDS C. A. Angell, J. Non-Cryst. Solids 102, 205 (1988) [I. Chang and H. Sillescu] Stokes-Einstein equation: [A. Einstein, Annalen der Physik 17, 549 (1905)] B2O3 o-terphenyl v ? ? ?H * Estos son los datos de las 6 sustancias que presentó Kauzmann en su tiempo, escalados