Two crossover regions in the dynamics of glass forming epoxy resins

Abstract

Broadband dielectric spectroscopy, heat capacity spectroscopy (3omega method), and viscosimetry have been used to study the dynamic glass transition of two glass-forming epoxy resins, poly [(phenyl glycidyl ether)-co-formaldehyde] and diglycidyl ether of bisphenol-A. In spite of their rather simple molecular structure, the dynamics of these systems is characterized by two well-separated crossover regions where the relaxation times of main transition and the two secondary relaxations beta and gamma approach each other. The main transition has three parts: The a process at high temperature, the a(') process between the two crossover regions, and the alpha process at low temperatures. Both the gamma-crossover region [around a temperature T-c(gamma)similar to(1.4-1.5)T-g and a relaxation time tau(c)(gamma)approximate to10(-10) s] and the beta-crossover region [around T-c(beta)similar to(1.1-1.2)T-g and tau(c)(beta)approximate to10(-6) s] could be studied within the experimentally accessible frequency-temperature window. Different typical crossover properties are observed in the two regions. The gamma-crossover region is characterized by onset of the (a',alpha) process, with a relaxation time about one decade greater than that of the quasicontinuous (a,gamma) trace. The beta-crossover region is characterized, besides splitting of main andbeta relaxation times, by a change in the temperature dependence of the main-relaxation time as reflected by a bend in the Stickel plot of the continuous (a('),alpha) trace, the separation of individual temperature dependences of different transport properties such as impurity-ions diffusion coefficient and viscosity, and a temperature-dependent main relaxation time that starts to be in accordance (at lower temperatures) with the Adam-Gibbs model. The cooperativity of the main process between the gamma and beta crossover seems to be small. Below the beta crossover, cooperativity increases up to values of order N(alpha)similar to100 near T-g, and configurational entropy seems to correlate with the main relaxation time. (C) 2002 American Institute of Physics

Effect of high hydrostatic pressure on the dielectric relaxation in a non-crystallizable monohydroxy alcohol in its supercooled liquid and glassy states

“…64). Such a non-monotonic behavior of JG relaxation was observed for epoxide-based thermosetting polymers, 65 and polypropylene glycol. 66 The trend in these results also points towards the experimental observations of tripropylene glycol, 67 though the effect observed for 5-methyl-2-hexanol for a change in the slope of log τ vs. T for temperatures close to T g observed here is much bigger.…”

Strain-induced low-frequency relaxation in colloidal DGEBA/SiO2 suspensions

“…There is no discontinuity visible. From the literature (Corezzi et al 2002) , it is known that the low-molecular-weight glass former DGEBA verifies the Vogel-Fulcher-Tammann law. It follows that the corresponding horizontal shift factors obey the WilliamsLandel-Ferry (WLF) equation.…”

Influence of suspension viscosity on Brownian relaxation of filler particles

“…Due to the small molecular weight of the DGEBA molecules, entanglements leading to a rubbery plateau in rheological measurements are not expected. Wideband dielectric spectroscopy (Capaccioli et al 1998;Corezzi et al 2002) also does not give a hint to slow relaxation processes in pure DGEBA. The situation changes when adding nanoscaled filler particles to the DGEBA matrix: In previous works, Dannert et al (2015Dannert et al ( , 2014 have published data on a low-frequency relaxation process observed in colloidal suspensions formed by DGEBA and spherical silica nanoparticles.…”