High-resolution 23Na, 27Al and 29Si NMR spectroscopy of framework Aluminosilicate glasses

Oestrike, Richard; Yang, Weifeng; Kirkpatrick, R. James; Hervig, R. L.; Navrotsky, Alexandra; Montez, Bernard

doi:10.1016/0016-7037(87)90269-9

Cited by 213 publications

(177 citation statements)

References 37 publications

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“…Without decoupling, the 29Si resonance of albite glass with 5.8 wt.% F is at -100.8 ppm. Our 29Si data for the F-free albite glass are in close agreement with those of OESTRIKE et al (1987) and KOHN et al ( 1989). The effect of F on the 29Si spectra is probably due to the removal of some Al from the silicate network by complexing with F. As Al has a deshielding effect on the Si resonance in an alumosilicate network ( ENGELHARDT and MICHEL, 1987).…”

Section: Resultssupporting

confidence: 79%

Fluorine in silicate glasses: A multinuclear nuclear magnetic resonance study

Schaller

Dingwell

Keppler

et al. 1992

Geochimica et Cosmochimica Acta

151

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Abstract-Anhydrous nepheline, jadeite, and albite glasses doped with F as well as hydrous F-containing haplogranitic glasses were investigated using "F combined rotation and multiple-pulse spectroscopy; 19F + 29Si cross-polarization/magic angle spinning (MAS); and high-power r9F decoupled 29Si, 23Na, and 27A1 MAS nuclear magnetic resonance methods. Fluorine preferentially coordinates with Al to form octahedral AIF:-complexes in all glasses studied. In addition, F anions bridging two Al cations, units containing octahedral Al coordinated by both 0 and F, or tetrahedral Al-F complexes might be present. The presence of Si-F bonds cannot be entirely ruled out but appears unlikely on the basis of the 19F + 29Si CP/MAS spectra. There is no evidence for any significant coordination of F with alkalis in the glasses studied. 23Na spectra are identical for the samples and their F-free equivalents and the spectra do not change upon decoupling of 19F. The speciation of F in the hydrous and anhydrous glasses appears to be very similar. Over the range of F contents studied (up to 5 wt.%), there seems to be hardly any dependence of F speciation on the concentration of F in the samples. The spectroscopic results explain the decrease of the viscosity of silicate melts with increasing F content by removal of Al from bridging AlO,-units due to complexing with F, which causes depolymerization of the melt. The same mechanism can account for the shift of the eutectic point in the haplogranite system to more feldspar-rich compositions with increasing F content, and for the peraluminous composition of most F-rich granites. Liquid immiscibility in F-rich granitic melts might be caused by formation of (Na,K),AlF, units in the melt with little or no interaction with the silicate component.The presence of F in granitic melts might increase the solubility of high field strength cations by making nonbridging 0 atoms available which form complexes with these cations. INTRODLJCPIONFLUORINE IS ONE OF THE MOST important volatile components of natural magmas, both in mantle-derived melts (e.g., lamproites) and in highly fractionated granitic magmas. Concentrations of several wt.% are reported in high-fluorine rhyolites (CONGDON and NASH, 1988) and in ongonites ( KOVALENKO, 1973). Similar to water, the presence of F strongly reduces the viscosity of silicate melts ( DINGWELL et al., 1985;DINGWELL, 1989) and increases diffusion coefficients ( DINGWELL, 1985). Even small amounts of F in the order of 1 wt.% will therefore significantly change the transport properties, mobility, and eruption behavior of such magmas. The correlation between high concentrations of certain trace elements (Sn, Zr, Nb, Ta, U, Th, etc.) and high F contents in granites and granitic pegmatites (STEMPROK, 1982) has stimulated the investigation of phase equilibria in F-containing granitic systems. MANNING ( 198 1) has shown that F strongly lowers both solidus and liquidus temperatures in the haplogranite system and causes a shift of the eutectic point towards more feldspar-rich...

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Section: Resultssupporting

confidence: 79%

Fluorine in silicate glasses: A multinuclear nuclear magnetic resonance study

Schaller

Dingwell

Keppler

et al. 1992

Geochimica et Cosmochimica Acta

151

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“…The spectra of G2 and G3 glazes consist of a peak at 55 ppm which is assigned to AlO 4 [27]. The broader low intensity peak around 0 ppm in these samples is a spinning sideband.…”

Section: Al Mas Nmrmentioning

confidence: 93%

“…The data acquisition conditions were a pulse width of 1.5 s (corresponding to a tip angle of ~30 o ), a pulse delay of 20 s, which produced relaxed spectra, with 800 scans co-added. 27 Al MAS NMR spectra were recorded using a Bruker Advance II + spectrometer equipped with a 14.1 T magnet (156.37 MHz for 27 Al). For the experiment the samples were packed into 3.2 mm zirconia rotors and spun at 18 kHz.…”

Section: Methods Of Characterizationmentioning

confidence: 99%

“…The 27 Al spectral data are given in table 3. The FWHM of 27 Al peaks are not reported, because this nucleus experiences second-order quadrupolar peak broadening [26]. The precision and accuracy is about ±1 ppm for the chemical shift and ±2% for the intensity.…”

Section: Al Mas Nmrmentioning

confidence: 99%

“…The peak of 70 ppm for G1 glaze can be assigned to Q 1 . 27 Al MAS NMR is used for examining the coordination of aluminum atoms in both polycrystalline and amorphous materials, but a detailed quantitative analysis of the spectra is more difficult to due second-order quadrupole effects [17]. The chemical shift for aluminum is around 50-80 ppm for AlO 4 , 10-15 ppm for AlO 6 and 30-40 ppm for AlO 5 , in well crystallized compounds [17].…”

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confidence: 99%

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Structure property relations in multicomponent oxide systems with additions of TiO2 and ZrO2 for glaze applications

Atkinson¹,

Teoreanu²,

Mocioiu³

et al. 2010

Journal of Non-Crystalline Solids

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The influence of the additives (10 weight% rutile, anatase and zirconia) on the atomic scale structure and microstructure of a base glaze (60 wt% feldspar, 15 wt% quartz, 8 wt% kaolin, 12 wt% dolomite and 5 wt% zinc oxide) are investigated. The morphology and structure of the glazes were determined by Scanning Electron Microscopy, X-ray diffraction, infra-red spectroscopy, as well as 27 Al and 29 Si magic angle spinning (MAS) NMR. Microscopy and X-ray diffraction revealed that the opacity was caused by crystals formed during thermal treatment. Although there are clearly crystalline phases present NMR shows that the heat treated glazes are dominated by the glassy component meaning the opacity is largely conveyed by the added oxide. The relationship between composition, structure and thermal expansion coefficient of the glazes is examined.

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