No abstract

Near-infrared spectroscopy was used to quantify the cure reaction of 4,4′-methylene- bis-(2,6-diethylaniline) (MDEA)–epoxy resins (E/A = 1.4) carried out at 72 and 160 °C. The absorption bands of the functional groups of interest in MDEA–epoxy resins are assigned according to the literature. A new assignment at 6580 cm−1 is also proposed for the secondary amine: it was supported by a synthesized model compound. Two different spectrum treatments were proposed. The first one is based only on a normalization at 4610–4620 cm−1, while the second one needs the subtraction of the normalized spectrum of a post-cure sample. To follow the curing process, amines and epoxy were studied at the same time in the combination and the overtone regions. The results are compared. In the combination region, quantitative results are obtained from absorbance measurements, while in the overtone region spectrum decompositions and area measurements are necessary. Complementary and reliable information are so obtained and allow us to calculate conversions of epoxide and amine I and concentrations in amine II, amine III, hydoxyl groups, and ether links. Kinetics are also established. The curing process mechanism is at last discussed for both curing temperatures.

No abstract

The construction of molecular models of crosslinked polymers is an area of some difficulty and considerable interest. We report here a new method of constructing these models and validate the method by modelling three epoxy systems based on the epoxy monomers bisphenol F diglycidyl ether (BFDGE) and triglycidyl-p-amino phenol (TGAP) with the curing agent diamino diphenyl sulphone (DDS). The main emphasis of the work concerns the improvement of the techniques for the molecular simulation of these epoxies and specific attention is paid towards model construction techniques, including automated model building and prediction of glass transition temperatures (Tg). Typical models comprise some 4200–4600 atoms (ca. 120–130 monomers). In a parallel empirical study, these systems have been cast, cured and analysed by dynamic mechanical thermal analysis (DMTA) to measure Tg. Results for the three epoxy systems yield good agreement with experimental Tg ranges of 200–220°C, 270–285°C and 285–290°C with corresponding simulated ranges of 210–230°C, 250–300°C, and 250–300°C respectively.

Thermoset (TS) epoxy resins can be toughened with a thermoplastic (TP) for high-performance applications. The final structure morphology has to be controlled to achieve high mechanical properties and high impact resistance. Four polyethersulfone-modified epoxy resins are considered. They consist of different epoxy monomer structure (TGAP, triglycidyl-p-aminophenol and TGDDM, tetraglycidyl diaminodiphenylmethane) and a fixed amount of thermoplastic, and they are cured with two different amounts of curing agent. A reactioninduced phase separation occurs for all formulations generating morphologies, different in shapes and scales. The aim is to control the final morphology and in particular its dominant length scale. This morphology depends on the phase separation process, from the initiation to its final stage. The initiation relies on the relative miscibility of the components and on the stoichiometry between epoxy and curing agent. The kinetics depends on the viscosity of the systems. The different morphologies are characterized by electron microscopy or neutron scattering. Dynamic mechanical analysis allows confirming the presence of a phase separation even when it is not observable by electron microscopy.Vermicular morphologies with few hundreds nanometer width are obtained for the systems containing the TGAP as epoxy monomer. Systems formulated with TGDDM presents morphologies on much smaller scale of order a few tens of nanometers. We interpret the different sizes of the morphologies as a consequence of a larger viscosity for the TGDDM systems as compared to the TGAP ones rather than by a latter initiation of phase separation. K E Y W O R D S epoxy resins, morphology, polymer blends, toughening