Glass enthalpy

Table 1. DSC melting point, melting enthalpy, glass transition temperate and heat capacity jump. 

The heat capacity of thiazole was determined by adiabatic calorimetry from 5 to 340 K by Goursot and Westrum (295,296). A glass-type transition occurs between 145 and 175°K. Melting occurs at 239.53°K (-33-62°C) with an enthalpy increment of 2292 cal mole and an entropy increment of 9-57 cal mole °K . Table 1-44 summarizes the variations as a function of temperature of the most important thermodynamic properties of thiazole molar heat capacity Cp, standard entropy S°, and Gibbs function - G°-H" )IT. 

Figure 4.3b is a schematic representation of the behavior of S and V in the vicinity of T . Although both the crystal and liquid phases have the same value of G at T , this is not the case for S and V (or for the enthalpy H). Since these latter variables can be written as first derivatives of G and show discontinuities at the transition point, the fusion process is called a first-order transition. Vaporization and other familiar phase transitions are also first-order transitions. The behavior of V at Tg in Fig. 4.1 shows that the glass transition is not a first-order transition. One of the objectives of this chapter is to gain a better understanding of what else it might be. We shall return to this in Sec. 4.8. 

These techniques help in providing the following information specific heat, enthalpy changes, heat of transformation, crystallinity, melting behavior, evaporation, sublimation, glass transition, thermal decomposition, depolymerization, thermal stability, content analysis, chemical reactions/polymerization linear expansion, coefficient, and Young s modulus, etc. 

The number of defects is maximal in the amorphous and liquid states. The phase diagram in Figure 5 shows the volume-temperature relationships of the liquid, the crystalline form, and the glass (vitreous state or amorphous form) [14], The energy-temperature and enthalpy-temperature relationships are qualitatively similar. 

Figure 5 Changes in volume, V, energy, E, and enthalpy, H, during cooling or heating of the liquid, crystalline, and glassy (vitreous) forms of a substance. Tm is the melting point, and Ts is the glass transition temperature. (Adapted with permission from Ref. 14.)...

The members of Class II in Table 1 present very small enthalpies of the mesophase-liquid transition [ AHml < 0.5 kJ/(mol of chain bonds)], suggesting that their mesophase is hardly stabilized by specific interatomic interactions. By contrast, we point out that in all cases the crystal-mesophase transition has a significant enthalpy value, mostly AHqm > 1 kJ/(mol of chain bonds). Consistent with their relatively flexible character, the polymers listed in the Tables have their glass transition below ambient temperature. 

Chung, H.-J., Lee, E.-J., and Lim, S.-T. (2002). Comparison in glass transition and enthalpy relaxation between native and gelatinized rice starches. Carbohydr. Polym. 48, 287-298. 

A sample of the polymer to be studied and an inert reference material are heated and cooled in an inert environment (nitrogen) according to a defined schedule of temperatures (scanning or isothermal). The heat-flow measurements allow the determination of the temperature profile of the polymer, including melting, crystallization and glass transition temperatures, heat (enthalpy) of fusion and crystallization. DSC can also evaluate thermal stability, heat capacity, specific heat, crosslinking and reaction kinetics. 

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