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 ▲]

The generalized Cauchy relation: a probe for local structure in materials with isotropic symmetry.

in Journal of Physics. Conference Series (2006), 40

The elastic properties of the isotropic state of condensed matter are given by the elastic constants ell and c44. In the liquid state the static shear stiffness c44 vanishes whereas at sufficient high ... [more ▼]

The elastic properties of the isotropic state of condensed matter are given by the elastic constants ell and c44. In the liquid state the static shear stiffness c44 vanishes whereas at sufficient high probe frequencies a dynamic shear stiffness may appear. In that latter case the question about the existence of a Cauchy relation appears. It will be shown that a pure Cauchy relation can appear only under special conditions which are rarely fulfilled. For all investigated materials, including ceramics, liquids and glasses, a linear relation between ell and c44 called generalized Cauchy relation is observed, which, surprisingly, follows a linear transformation. [less ▲]

Gradient of the Mechanical Modulus in Glass-Epoxy-Metal Joints as Measured by Brillouin Microscopy.

in Journal of Adhesion (2004), 80(7), 585-599

The newly developed Brillouin microscopy is used for the first time to measure in situ the longitudinal elastic stiffness coefficient in the GHz-range inside of glass-epoxy-metal joints as a function of ... [more ▼]

The newly developed Brillouin microscopy is used for the first time to measure in situ the longitudinal elastic stiffness coefficient in the GHz-range inside of glass-epoxy-metal joints as a function of distance from the substrates. Interphases with a local variation of mechanical properties are quantitatively characterized. These interphases possess unexpected widths of tens to hundreds of microns. Inside the interphases, the spatial variation of the longitudinal stiffness coefficient depends on the type of substrate, on the curing conditions for the epoxy and probably on the distribution of internal stresses. The obtained spatial mechanical profiles provide valuable insight into the morphology-driven mechanics of the interphase, but additional information is needed for a full understanding of their physical and chemical origin. The presented results prove the sensitivity of the Brillouin microscopy; the elastic stiffness coefficients are detected with an accuracy in the subpercentage range. The spatial resolution is better than 10 µm. [less ▲]

Cauchy-like relation between elastic constants in amorphous materials.

in Physical Review. B, Condensed Matter and Materials Physics (2002), 66(1), 012206-012210

It is well known that in addition to the longitudinal modulus, viscoelastic liquids show a shear stiffness at sufficiently high probe frequencies due to structural relaxations. For probe frequencies that ... [more ▼]

It is well known that in addition to the longitudinal modulus, viscoelastic liquids show a shear stiffness at sufficiently high probe frequencies due to structural relaxations. For probe frequencies that are large compared to the structural relaxation frequency, the measured elastic longitudinal and shear moduli become so-called clamped properties (c11∞ and c44∞, respectively). During freezing or polymerization of amorphous liquids, these clamped moduli behave in a strongly nonlinear fashion as a function of temperature or polymerization time. Based on Brillouin spectroscopy data we will show that there exists a linear relation between c11∞ and c44∞ over a large temperature or polymerization time range. Surprisingly, the parameters of this linear relation between the elastic moduli vary only little for different materials. Implications for the nonlinear elastic behavior at the glass transition will be discussed on the basis of mode Grüneisen parameters. [less ▲]