Several reasons are given to assume both the maximum of thermally stimulated depolarization near 100 °C and the thermovoltaic effect in aluminophosphate glasses to be associated with the movement of protons. The assumption, that the glasses are hydrolyzed, is supported by this finding.

On the relation between thermally stimulated depolarization and thermoelectricity in irradiated aluminophosphate glasses

The absorption and ESR spectra of multicomponent alumino-phosphate glasses doped with manganese (0·2–20 mol %) has been measured and compared with the absorption spectra of manganous and manganic ions in model solutions. The unirradiated glasses show in ultraviolet region increasing absorption below 200 nm with the shoulder at 235 nm and the absorption bands due to manganous oxygen complexes in octahedral symmetry. They are similar to the absorption bands of Mn2+ in concentrated H3PO4 acid. In irradiated glasses the bands at 200, 235, 275 (only if Mn is present) and a broad band at 540 nm appear. After the annealing at 450 C all radiation-induced bands disappear and the bands at 235 nm is more pronounced. The Mn3+ in H3PO4 solution exhibit the absorption spectrum with a weak band at 530 nm and a very intense band at 270 nm. It is therefore proposed that both the 540 and 275 nm bands in irradiated glasses can be assigned to octahedral oxygen complexes of Mn3+, i.e. to hole centres. The band at 200 nm which is practically independent of the modifiers (Be, Mg, Ca, Sr and Ba) is, therefore, associated with electron centres (electrons trapped in non-bridging oxygen vacancies). It is suggested that the band at 235 nm in irradiated and annealed glasses is associated with irreversible structural changes.

Absorption phenomena in multicomponent phosphate glasses with Mn

Optical absorption in broad frequency range (150−5×104 nm) and thermoluminiscence (TL) of the manganese doped alumino-phosphate glasses with two modifiers (Mg, Sr) were measured. It was found that with prolonged melting time the absorption bands at 3·1 μm, 5·3 and 5·9 μm decrease, new band at 4·2 μm appears and that one in UV at about 235 nm increases. Simultaneously the solubility of the glasses in water increases. At longer melted and irradiated glasses the band of electron centres at 210 nm increases while that one of hole centres at 550 nm decreases. These changes are due to the escape of water bonded on two non-bridging oxygens, as well as to the hydrolysis of the melt and oxidation of divalent magnanese. The role of modifiers is also pointed out.

On the role of water in some optical properties of alumino-phosphate glasses containing manganese

Low temperature photoluminescence of NaCl-Ni crystals

ESR study of multicomponent phosphate glasses

The emission spectra both of fluorescence at room temperature and at 520 K and of thermostimulated luminescence (TSL) of multicomponent alumino-phosphate glasses with various Mn concentration (0·2–20mol%) has been measured. The colour of fluorescence and TSL changes from orange to yellow with increasing temperature at constant concentration of Mn and from yellow to red with increasing concentration at constant temperature. The colour shift with temperature can be explained by means of decreasing field strength, Dq with increasing distance Mn-O. The intensity of orange fluorescence at R.T. increases with increasing concentration up to about 5% Mn and then decreases in consequence of concentration quenching. On the contrary, the TSL intensity reaches its maximum at concentraction of about one order of magnitude smaller. The different behaviour of fluorescence and TSL intensity in dependence on Mn is probably due to their different elementar mechanisms.

Luminescence of multicomponent phosphate glasses with manganese

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Luminescence of multicomponent phosphate glasses with manganese