Kinetics of Mesophase Transitions

The kinetics of the mesophase transitions can be discussed by comparison with the crystallization-melting and the vitrification-devitrification transitions of the three limiting phases of Fig. 2. Except for the crystallization kinetics, the literature on the kinetics of phase transitions is limited. For the mesophases, information is scarce. 

Both of these polymers do not have any reported mesophase. Since the glass transition is a freezing process on a 3 to 10 mobile unit (bead) scale, there are neither phase boundaries nor nucleation barriers for the process. 

Price and Wendorff31 and Jabarin and Stein 32) analyzed the solidification of cholesteryl myristate. Under equilibrium conditions it changes at 357.2 K from the isotropic to the cholesteric mesophase and at 352.9 K to the smectic mesophase (see Sect. 5.1.1). At 346.8 K the smectic liquid crystal crystallized to the fully ordered crystal. Dilatometry resulted in Avrami exponents of 2, 2, and 4 for the respective transitions. The cholesteric liquid crystal has a second transition right after the relatively quick formation of a turbid homeotropic state from the isotropic melt. It aggregates without volume change to a spherulitic texture. This process was studied by microscopy32) between 343 and 355.2 K and revealed another nucleation controlled process with an Avrami exponent of 3. 

Adamski and Klimczyk analyzed cholesteryl pelargonate36) and caproate 37) liquid crystal to fully-ordered-crystal transitions over a temperature range of about 25 K. Again, the appearance of the fully ordered crystals was that of a spherulitic superstructure. The nucleation was time dependent, and the linear growth rate of the spherulites decreased with decreasing temperature by a factor 1/2 to 1/3, in contrast to the nonanoate and acetate. The Avrami exponent was close to 4 as judged from the measurement of the crystallized volume in the field of view under the microscope. 

The kinetics of transition from the liquid crystal to the fully ordered crystal of flexible, linear macromolecules was studied by Warner and Jaffe 38) on copolyesters of hydroxybenzoic acid, naphthalene dicarboxylic acid, isophthalic acid, and hydro-quinone. The analytical techniques were optical microscopy, calorimetry and wide angle X-ray diffraction. Despite the fact that massive structural rearrangements did not occur on crystallization, nucleation and growth followed the Avrami expression with an exponent of 2. The authors suggested a rod-like crystal growth. 

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Cheng SZD (1988) Kinetics of mesophase transitions in thermotropic copolyesters. 1 calorimetric study. Macromolecules 21 2475... 

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