Influence of Nanoparticles on the Coupling Between Optical Dipoles in Epoxy-Silica Nanocomposites During Network Formation

in The Journal of Adhesion (2012), 88(7), 566-588

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 ... [more ▼]

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. [less ▲]

Shelf Life and Controlled Cure of Epoxies by Loaded Zeolite

in Composite Interfaces (2010)

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 ... [more ▼]

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. [less ▲]

Second order elasticity at hypersonic frequencies of reactive polyurethanes as seen by generalized Cauchy relations.

in Journal of Physics : Condensed Matter (2009), 21

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 ... [more ▼]

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. [less ▲]

Chemically induced transition phenomena in polyurethanes as seen from generalized mode Grüneisen parameters.

in Journal of Physics : Condensed Matter (2008), 20(20), 205101-205108

Many phenomenological properties of reactive polymers like polyurethanes increase or decrease continuously in the course of the curing process before saturating at the end of the chemical reaction. This ... [more ▼]

Many phenomenological properties of reactive polymers like polyurethanes increase or decrease continuously in the course of the curing process before saturating at the end of the chemical reaction. This holds true for instance for the mass density, the refractive index, the chemical turnover and the hypersonic properties. The reason for this monotone behaviour is that the chemical reaction behaves like a continuous succession of irreversible phase transitions. These transitions are superposed by the sol–gel transition and possibly by the chemically induced glass transition, with the drawback that the latter two highlighted transitions are often hidden by the underlying curing process. In this work we propose generalized mode Grüneisen parameters as an alternative probe for elucidating the polymerization process itself and the closely related transition phenomena. As a model system we use polyurethane composed of a diisocyanate and varying ratios of difunctional and trifunctional alcohols. [less ▲]

About the nature of the structural glass transtion: an experimental approach

in Henkel, M.; Pleimling, M.; Sanctuary, Roland (Eds.) Aging of the Glass Transition (2007)

The nature of the glassy state and of the glass transition of structural glasses is still a matter of debate. This debate stems predominantly from the kinetic features of the thermal glass transition ... [more ▼]

The nature of the glassy state and of the glass transition of structural glasses is still a matter of debate. This debate stems predominantly from the kinetic features of the thermal glass transition. However the glass transition has at least two faces: the kinetic one which becomes apparent in the regime of low relaxation frequencies and a static one observed in static or frequency-clamped linear and non-linear susceptibilities. New results concerning the so-called ?-relaxation process show that the historical view of an unavoidable cross-over of this relaxation time with the experimental time scale is probably wrong and support instead the existence of an intrinsic glass transition. In order to prove this, three different experimental strategies have been applied: studying the glass transition at extremely long time scales, the investigation of properties which are not sensitive to the kinetics of the glass transition and studying glass transitions which do not depend at all on a forced external time scale. [less ▲]

Complex specific heat capacity of two nanocomposite systems

in Thermochimica Acta (2006), 445(2), 111-115

Thermal investigations on two selected model-nanocomposites have been made. They differ with regard to the type of the anorganic nanoparticles that have been filled into an organic oligomer matrix. The ... [more ▼]

Thermal investigations on two selected model-nanocomposites have been made. They differ with regard to the type of the anorganic nanoparticles that have been filled into an organic oligomer matrix. The properties of nanocomposites may vary between those of a simple mixture of independent components and those of a system, where specific interfacial interactions between the constituting parts lead to ‘new’ properties. Depending on the type of the nanoparticles filled into the matrix, the resulting properties might be closer to one or to the other extreme. We used temperature modulated differential scanning calorimetry (TMDSC) to investigate a matrix of the oligomer diglycidyl ether of bisphenol A (DGEBA) filled either with SiO2- or Al2O3-nanoparticles. The dependence of the complex specific heat capacity () on the concentration of nanoparticles shows a clear difference between the two systems as far as the glass transition of the oligomer is concerned. The SiO2 composite seems to behave more like a simple mixture, whereas the Al2O3 composite shows ‘new’ properties. [less ▲]

Mechanical Interphases in Epoxies as seen by Nondestructive High-Performance Brillouin Microscopy

in Adhesion - Current Research and Application (2005)

Acoustic profilometry within polymers as performed by Brillouin microscopy

in Journal of Physics : D Applied Physics (2003), 36(21), 2738-2742

Using high performance Brillouin spectroscopy we present a new technique, which enables us to perform acoustic microscopy with a spatial resolution of about 1 μm. This technique, called Brillouin ... [more ▼]

Using high performance Brillouin spectroscopy we present a new technique, which enables us to perform acoustic microscopy with a spatial resolution of about 1 μm. This technique, called Brillouin microscopy, is tested on several bulk- and film-like polymer samples. [less ▲]