Evaluation of the reversible contribution to the reversing heat capacity in isotactic polystyrene

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• 作者：Hui Xu and Peggy Cebe
• 关键词：Reversing heat capacity ; Isotactic polystyrene ; Differential scanning calorimetry
• 刊名：Thermochimica Acta
• 出版年：2006
• 出版时间：15 March 2006
• 年：2006
• 卷：442
• 期：1-2
• 页码：42-47
• 全文大小：157 K

文摘

We report the results of time dependent analysis of the reversing heat capacity peaks in isotactic polystyrene (iPS). Solution grown crystals (SGCs) and bulk films of iPS were examined using quasi-isothermal temperature modulated differential scanning calorimetry (QI-TMDSC). Both types of iPS samples showed two reversing heat capacity peaks as reported before [H. Xu, P. Cebe, Macromolecules 37 (2004) 2797; H. Xu, P. Cebe, Macromolecules 38 (2005) 770], and the two peaks are associated with melting of different portions of crystal lamellae with different degree of thermal stability [T. Liu, J. Petermann, Polymer 42 (2001) 6453]. Here, the behavior of the reversing heat capacity is studied as a function of holding time from the establishment of steady state, until the end of the quasi-isothermal holding period. The reversing heat capacity decreases with time at each of the two peak positions. For both types of iPS (SGC and bulk film) the time dependence of each of the reversing heat capacity peaks is fitted using C_p(t) = C_p∞ + A₁ exp(−t/τ₁) + A₂ exp(−t/τ₂). The fit parameters (equilibrium reversible heat capacity, C_p∞; prefactors, A₁ and A₂; relaxation times, τ₁ and τ₂) provide a means to compare the decay of the dual reversing heat capacity peaks of iPS solution grown crystals with bulk cold-crystallized film. Results show that iPS bulk films have longer relaxation times (τ₁ and τ₂) and smaller C_p∞ value than the iPS SGCs. Both results suggest that the iPS bulk films have higher degree of crystal perfection than SGCs.