Mossbauer spectra of tin in binary Si-Sn oxide glasses

Abstract

The Massbauer spectra of in binary glasses of SnO and Si%, in varying proportions of between 16.8 and 71.5 mol% SnO. have been obtained at 77 K. From these spectra the tin was found to be predominantly in the 2"' state. The isomer shift and the quadrupole splitting were both significantly p a t e r than those in crystalline SnO and were found to decrease with increasing tin content. which also corresponds to decreasing molar volume. A second series of spectra of two of the san&.s was taken at temperatures between 10 and 300 K. These spectra show a decrease in shift with temperature which was the same for the two samples and which could only partly be accounted for by the second-order Doppler shift. The remainder was ascribed to the temperature dependence of the isomer shih. By using these data together with the measured expansivity and increase in density with tin content. it was possible CO wrrect the isomer shift for the effects of the change in volume, and it was found that the volumesorrected isomer shift inereared with increasing tin content. This showed that there was an increase in s-electron density at the tin nuclei. while the accompanying decrease in quadrupole splitting showed a decrease in the p-electron character, as expected for a decrease in covalency. From the decrease in absorption area with temperature the Debye temperature of tin was estimated to be -190 K, which is slightly less than that of crystalline SnO, and decreased with increasing tin content, All the data suggest that the Sn-0 bonds become progressively less covalent as more tin is added to SnO-Si% glasses, and possibly indicate a change from 4-fold to &fold co-ordination.A third series of spectra was obtained for the glass containing 40.9 mol% of SnO after a series of heat trements. The spectra show changes in the oxidation state of the tin which depended upon the different conditions applied.

119mSn Mössbauer studies on tin compounds

“…Tin in glasses has been found to consist mainly of Sn" in binary materials SiOrSn and in float glass, while Sn IV predominates in remelted specimens of SiOrSnO; the percentage SnII/Sn IV was estimated by the magnitude of 'I' factors calculated from variable temperature 119Sn M6ssbauer spectroscopy [150], the dynamics of tin nuclei being investigated [151]. Further work concerned arsenic-selenium-tin glasses [152], potassium-tin germanate glasses [153] and tin borate glasses [154], information being obtained on the tin valence state (SnII, Sn IV ), the relative percentage and the geometry of tin environments, as a function of sample preparation and treatment.…”

Nanomechanical properties of commercial float glass

“…The structure of amorphous SnO and SnO 2 were determined to be distorted versions of the crystalline structure [15]. It has been established that the majority of Sn 2+ in silicate glasses is coordinated to three oxygens in a pseudo-tetrahedral arrangement, with a lone pair of electrons occupying the fourth orbital [12][13][14][16][17][18][19][20][21][22][23][24][25][26], but a small number of the Sn 2+ in binary tin silicate glasses are coordinated to four oxygens in a square pyramidal arrangement [18]. The number of four-coordinated tin decreases as the tin content is increased.…”

Effect of tin-oxide on the physical properties of soda-lime–silica glass

“…The local chemical structure of binary and ternary silicate glasses containing tin has been investigated using Mö ssbauer spectroscopy, nuclear magnetic resonance, and neutron diffraction [13,[19][20][21][22][23][24][25]. Those studies also addressed glasses with relatively high concentrations of tin in the glass (16-70 mol%), and it remains to be determined how the character of the tin in those glasses relates to the tin-enriched layer of commercial sodalime-silicate float glass, which possesses a substantially lower tin concentration.…”