Interfacial chemistry and adhesive durability

The improved understanding of adsorption chemistry which has arisen from the development of new surface analytical techniques during the last twenty years has had a major effect on the understanding of catalytic reaction mechanisms. However, there are many other areas of technology where Interfacial chemistry has a determining role but where the understanding is much less developed. In this paper examples are presented of the role of interfacial chemistry in adhesion. In particular, It Is shown that modification of a surface to the extent of just a few atomic layers in depth can have dramatic effects on the performance of adhesive bonds, particularly when exposed to hostile environmental conditions. These examples will be used to highlight a need for greater fundamental understanding of the interfacial chemistry of adhesion and also other technologies where interface effects are dominant.     

Energy dissipation via radiative recombination and vibronic relaxation in σ-delocalized silicon backbone network polymers

The nature of ultrafast energy dissipation in poly(n-hexylsilyne), a prototypical σ-delocalized alkysilicon network polymer, is explored. This disordered silicon backbone material exhibits strong near-UV to visible band-edge absorption and a high quantum yield of visible emission. The time evolution of the emission band is studied over four decades of time using time-resolved luminescence as a probe. The data indicate that while there is an ‘intrinsic’ Stokes shift after photoexcitation due to kinetic energy relaxation (<10ps), thermalization within a dense band of vibronic states via intramolecular phonon-assisted hopping on a nanosecond timescale is the dominant mechanism for excited-state decay. The data can be understood in terms of theoretical predictions for energy relaxation in disordered materials.     

Analysis of the fluorescence of the ion Eu in fluoroborate glasses containing silver particles

We have studied theoretically and experimentally the fluorescence enhancement in fluoroborate glasses, doped with the ion Eu³⁺, containing small silver particles. The model developed shows that the gain coefficient has quenching and enhancement regions. The absorption peak of the metallic particles occurs at 425 nm, which is not in resonance with the ⁵L₆ level of the ion Eu³⁺. For this reason it is not possible to make a complete comparison between theoretical and experimental results, but the structure of the absorption spectra allows us to check some crucial aspects of the problem, such as energy transfer, enhancement of the local field and the high absorption by the particle system. Results of electronic microscopy have revealed non-uniformity of the particle distribution with average radii of approximately 20 Å and 35 Å and a measured localized mean filling factor of 0.02.     

Absorption spectra of solid rare earth complexes obtained from the inner filter effect on luminescence

The inner filter effect is observed in luminescence whenever a second substance is present that has absorptions which overlap the luminescence. This results in a diminution of the luminescence at those wavelengths and is generally observed in solution. In the present communication we show that this effect can be observed when a solid rare earth complex is physically mixed with a solid luminescent organic matrix with which it does not interact. The resulting luminescence is reduced in emission intensity at those wavelengths corresponding to the absorptions of the rare earth ion. This is illustrated with a mixture of Na₃[Ho(ODA)₃] ·2NaClO₄·6H₂O and pyrene at 77 K, and it is shown that the absorption spectrum of the holmium complex can be extracted from the luminescence spectrum of pyrene. This absorption spectrum is in good agreement with that obtained by conventional spectroscopy with a single crystal.