화학공학소재연구정보센터
Journal of Polymer Science Part B: Polymer Physics, Vol.56, No.20, 1393-1403, 2018
A structural interpretation of the two components governing the kinetic fragility from the example of interpenetrated polymer networks
Kinetic fragility and cooperativity length, two major characteristics of the relaxation dynamics at the glass transition, are, respectively, investigated by dynamic mechanical analysis and modulated temperature differential scanning calorimetry in a series of interpenetrated polymer networks based on acrylate and epoxy systems. The relaxation dynamics are impacted by two variables: the rigidity of the network, and the structural heterogeneity resulting from blending. However, the fragility and the cooperativity do not vary similarly. The glass transition progressively broadens as the mass fractions of acrylate and epoxy become equivalent, leading to a strong decrease in cooperativity. On the other hand, under the same conditions, the fragility transitions between the lower value of pure acrylate and the higher value of pure epoxy. This divergence helps concluding that the variations in the temperature dependence of the relaxation time are not purely related to the more or less cooperative nature of the glass transition. By splitting the fragility index in a volume contribution and an energetic contribution, it is shown that the contribution of cooperativity to the variations of the relaxation time with temperature is increased under two structural conditions: low backbone rigidity and high intermolecular interactions. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 1393-1403