Evolution of vibrational properties during a macromolecule's growth.
The elastic constants and vibrational contributions to thermal properties of three polymerizing liquids were investigated by using the available hypersonic velocity measured by Brillouin light scattering in real time. During the addition polymerization to a molecular network structure, Poisson's ratio upsilon(Poisson) decreases approximately according to exp[-(kt(polym))]n, where both k and n are composition dependent. The Debye frequency increases and the corresponding heat capacity, energy, and entropy approaching a limiting value. upsilon(Poisson) of the vitrified polymer continues to decrease but much more slowly, indicating its continued slow polymerization and structural relaxation with time. In the potential energy landscape interpretation, a polymerizing liquid's state point continuously shifts to another landscape's more curved, deeper minima.
Johari
G P
GP
Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario L8S 4L7, Canada. joharig@mcmaster.ca
Wen
Ping
P
Venkateshan
K
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