STRUCTURE OF SODIUM ALUMINOSILICATE GLASSES : T1 LUMINESCENCE SPECTROSCOPY

Abstract

Les spectres optiques des ions Tl+, correspondant à une émission à 350 nm, ont été mesurés dans des verres d'aluminosilicate de sodium. Les spectres mettent en évidence deux contributions dues respectivement à T1+ agissant comme modifieur du réseau ou comme compensateur de charge pour l'aluminium. Quand le rapport Al/Na devient plus grand que 1, le spectre de compensation de charge est seul observé. En dessous de 1, le spectre de modifieur du réseau prend de plus en plus d'importance quand Al/Na décroît. Ceci est bien en accord avec le modèle traditionnel des structures d'aluminosilicate alcalins, où la composition critique pour la disparition des oxygènes non-pontants est donnée par Al/Na = 1.Optical excitation spectra of Tl+ ions, corresponding to emission at 350 nm, have been measured in Na aluminosilicate glasses. The excitation spectra are shown to be superpositions of two primary spectra, which are identified with T1+ acting as network modifiers or as charge compensators for network aluminums. When Al/Na ≥ 1, only the charge compensator spectrum can be observed. As Al/Na decreases below unity, the fraction of the charge compensator spectrum decreases rapidly, and the fraction of the network modifier spectrum increases correspondingly. These results strongly support the traditional model of alkali aluminosilicate structure, in which the critical compositions for (dis)appearance of nonbridging oxygens are given by Al/Na = 1 ; they contradict reports of XPS measurements from which it had been concluded that the critical compositions are given by Al/Na ≈ 0.7. The network modifier spectra do not depend strongly on glass composition, whereas the charge compensator peaks vary significantly with composition. These results are fully consistant with new oxygen is XPS spectra

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