Glass transition of an epoxy resin induced by temperature, pressure and chemical conversion: a configurational entropy rationale

A comparative study is reported on the dynamics of a glass-forming epoxy resin when the glass transition is approached through different paths: cooling, compression, and polymerization. In particular, the influence of temperature, pressure and chemical conversion on the dynamics has been investigated by dielectric spectroscopy. Deep similarities are found in dynamic properties. A unified reading of our experimental results for the structural relaxation time is given in the framework of the Adam-Gibbs theory. The quantitative agreement with the experimental data is remarkable, joined with physical values of the fitting parameters. In particular, the fitting function of the isothermal tau(P) data gives a well reasonable prediction for the molar thermal expansion of the neat system, and the fitting function of the isobaric-isothermal tau(C) data under step- polymerization conforms to the prediction of diverging tau at complete conversion of the system.Comment: 16 pages, 8 figures, from the talk given at the 4th International Discussion Meeting on Relaxations in Complex Systems (IDMRCS), Hersonissos, Helaklion, Crete (Greece), 17-23 June 200

Vitrification during the Isothermal Cure of Thermosets: Comparison of Theoretical Simulations with Temperature-Modulated DSC and Dielectric Analysis

Vitrification during the isothermal cure of a thermoset, which is monitored by dynamic techniques such as temperature-modulated differential scanning calorimetry (TMDSC) or dielectric analysis (DEA), is analyzed in terms of its dependence on frequency. A simulation was used to obtain the vitrification time as a function of frequency, considering it as the time when the (frequency-dependent) glass transition temperature, Tg, of the curing system reaches the cure temperature. Simulations were carried out at different cure temperatures. Other parameters, such as the exponents (reaction orders) in the Kamal equation, l in the DiBenedetto equation (controlling the dependence of Tg on the degree of cure), and the activation energy for the frequency dependence of Tg, were also considered. The results are compared with those obtained experimentally by a TMDSC technique at low frequencies and by DEA at high frequencies. From the simulations it is found that the vitrification time decreases nonlinearly with log(frequency) in the low frequency range but approaches a linear dependence at high frequencies, in agreement with experimental data.Peer ReviewedPostprin