Stress-corrosion mechanisms in silicate glasses

The present review is intended to revisit the advances and debates in the comprehension of the mechanisms of subcritical crack propagation in silicate glasses almost a century after its initial developments. Glass has inspired the initial insights of Griffith into the origin of brittleness and the ensuing development of modern fracture mechanics. Yet, through the decades the real nature of the fundamental mechanisms of crack propagation in glass has escaped a clear comprehension which could gather general agreement on subtle problems such as the role of plasticity, the role of the glass composition, the environmental condition at the crack tip and its relation to the complex mechanisms of corrosion and leaching. The different processes are analysed here with a special focus on their relevant space and time scales in order to question their domain of action and their contribution in both the kinetic laws and the energetic aspects.Comment: Invited review article - 34 pages Accepted for publication in J. Phys. D: Appl. Phy

Rotation-tunnel de l'ammonium dans l' alumine β

We present a study of the NMR spectrum of protons belonging to ammonium ions in ammonium β-alumina, at low temperature. We show that ammonium ions in Beevers-Ross sites undergo a fast rotational tunnelling which gives rise to a strong narrowing of their NMR spectrum, while ammonium ions in mid-oxygen sites are static and give a broad spectrum. By examining a mixed sodium-ammonium sample, we have been able to separate the spectrum of Beevers-Ross ions. The theory of magnetic resonance of protons belonging to NH+4 ions submitted to a fast rotational tunnelling, as formalized by Lalowicz et al., is applied. It yields a very nice agreement with the experimental spectrum. This also allows the stable orientation of the NH4 tetrahedron in the Beevers-Ross site to be determined.Nous présentons une étude du spectre de résonance magnétique des protons appartenant aux ions NH+4 dans l'alumine β à l'ammonium, à basse température. Nous montrons que les ions en site Beevers-Ross sont soumis à une rotation-tunnel rapide qui se manifeste par un rétrécissement de la raie de résonance, alors que les ions en site mid-oxygen apparaissent comme statiques et donnent une raie large. En opérant sur un échantillon mixte sodium-ammonium, nous avons pu isoler le spectre des ions Beevers-Ross. L'application de la théorie du spectre des protons de l'ion ammonium dans le cas d'un rétrécissement par la rotation-tunnel, formalisée par Lalowicz et al., fournit une description remarquablement bonne des spectres expérimentaux et permet de déterminer l'orientation d'équilibre du tétraèdre NH4 dans le site Beevers-Ross