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High-performance refractometry and infrared spectroscopy are combined in order to elucidate the gelation process and the glass transition during the network formation of epoxies and epoxy-based nanocomposites. Whereas infrared spectroscopy yields the chemical conversion due to the opening of oxirane rings during the covalent network formation, high-performance refractometry is extremely sensitive to the accompanying changes of the arrangement of the molecular network. In accordance with the Lorentz-Lorenz relationship, the evolution of the refractive index seems to reflect that of the mass density during polymerization of the epoxy-based systems within the limits of a few percent. The slight deviations from the Lorentz-Lorenz relationship, which occur during the gelation of the epoxy-based systems, are attributed to long-ranged dipole-dipole interactions, which respond at optical frequencies. This point of view is supported by the fact that chemically inert silica nanoparticles embedded in the pure epoxy matrix as disturbances for these dipole-dipole interactions are able to diminish or even to suppress totally this excess contribution of the refractive index.

Structural developments are investigated in network-forming reactive polymers by time- and 10 space-resolved scanning Brillouin microscopy. Hypersonic properties are probed to reveal the subtle interplay between molecular transport, dissolution, polymerization and network defects in the vicinity of the interface between reactants, which are either pure epoxy resin or various epoxy resin-hardener mixtures, topped by a layer of pure hardener. The trans-interfacial polymerization produces heterogeneous epoxy structures of either gelatinous or glassy nature. Interestingly, the 15 hardener can easily penetrate and swell these networks and epoxy network fragments can be transported over several millimeters by convective flow. The observed features may be used to form interpenetrating networks during self-healing procedures.

Epoxy formulations based on the multi-functional amine hardener, dicyandiamide (Dicy), regularly contain a free accelerator for reducing the curing temperature and the time needed to complete the network formation. Unfortunately, all accelerators reduce the shelf life of these adhesives at 25◦C. In order to solve this problem, accelerator-loaded zeolites fillers were developed, optimised with respect to host–guest interactions and characterised by Fraunhofer IFAM (Bremen, Germany) with regard to the release and curing behaviour in epoxy adhesive formulations. They are added to an epoxy adhesive (diglycidylether of bisphenol A (EP) and dicyandiamide (Dicy), mass ratio 100:6.7), stored at 25◦C in regular air or cured (heated with β = 10 K/min to 170◦C subsequent isothermal curing for 45 min). That shelf life and curing behaviour are investigated by FT-IR spectroscopy and modulated DSC. Compared to the EP containing free accelerator, the zeolite-filled EP possesses a threefold increase in shelf life at 25◦C due to the immobilization of the accelerator in the pores of the zeolites. While the free accelerator acts steadily during heating, it is shown that the loaded zeolite releases the accelerator at about 76◦C. Surprisingly, the released accelerator is not only involved in the chemical formation of the epoxy network but it accelerates the dissolution of Dicy considerably. As the result, network formation at 170◦C finishes after not more than 19 min and the starting temperature for curing could be reduced to 140◦C.

The non-equilibrium process of polymerization of reactive polymers can be accompanied by transition phenomena like gelation or the chemical glass transition. The sensitivity of the mechanical properties at hypersonic frequencies—including the generalized Cauchy relation—to these transition phenomena is studied for three different polyurethanes using Brillouin spectroscopy. As for epoxies, the generalized Cauchy relation surprisingly holds true for the non-equilibrium polymerization process and for the temperature dependence of polyurethanes. Neither the sol–gel transition nor the chemical and thermal glass transitions are visible in the representation of the generalized Cauchy relation. Taking into account the new results and combining them with general considerations about the elastic properties of the isotropic state, an improved physical foundation of the generalized Cauchy relation is proposed.

Reactive network forming polymer systems like epoxies are of huge technological interest because of their adhesive properties based on specific interactions with a large variety of materials. These specific interactions alter the morphology of the epoxy within areas determined by the correlation length of these interactions. The changed morphology leads to interphases with altered (mechanical) properties. Besides these surface-induced interphases, bulk interphases do occur due to segregation, crystallization, diffusion, etc. A new experimental technique to characterize such mechanical interphases is μ-Brillouin spectroscopy (μ-BS). With μ-BS, we studied interphases and their formation in epoxies due to segregation of the constituent components and due to selective diffusion of one component. In the latter case, we will demonstrate the influence of changing the boundary conditions of the diffusion process on the shape of the interphase.