Rheokinetical behavior of melamine-formaldehyde resins

The effects of cure temperature and amount of catalyst on the rheokinetical behavior of a melamine-formaldehyde (MF) thermosetting system is investigated using a dynamic mechanical technique similar in nature to Torsion Impregnated Cloth Analysis (TICA) and Torsional Braid Analysis (TBA). The proposed name of the used technique is Torsional Substrate Analysis (TSA). Isothermal cures of the resin are carried out from 115°C to 160°C for varying amounts of catalyst. Each TSA measurement exposes several transitions. First, a glass-to-liquid transition during the heatup procedure is seen, indicated by sharp peaks of the loss shear modulus, G″, and loss tangent, tanδ. Later, vitrification is seen, indicated by a second G″ maximum. Finally, a completion of shift to a diffusion controlled cure reaction occurs, shown as a storage shear modulus, G′, plateau. The rheokinetical data is used to construct Time-Temperature-Transformation (TTT) cure diagrams, for each level of catalyst. High pressure differential scanning calorimetry (HPDSC) measurements are carried out in order to estimate the fractional conversion of samples that have been cured isothermally for times corresponding to a second tanδ maximum, the second G″ maximum, and the G′ plateau. The fractional conversion is determined by the residual entalphy technique. The HPDSC measurements do not give a clear answer whether the second tanδ maximum corresponds to gelation or not. It is therefore likely that TSA, like similar techniques, is not capable to detect gelation. A glass transition temperature of 130°C and 150°C is found to correspond to a fractional conversion of 0.65 and ∼0.80, respectively. Preliminary measurements suggest that the maximum glass transition temperature, Tg ∞, of the investigated MF resin is at least 180°C.