A note on the Raman spectra of water-bearing albite glasses

The Raman spectra of albite glasses with 4.5 and 6.6 weight percent water have been obtained, and are compared with that of a dry sample. The hydrous glasses show bands near 3600 cm^?1 due to O-H stretching, and a previously unreported weak band near 1600 cm^?1 due to bending of molecular H₂O. Other weak spectral features are discussed, and the effect of dissolved water on the aluminosilicate framework vibrations is considered.     

Application of infrared spectroscopy to studies of silicate glass structure: Examples from the melilite glasses and the systems Na2O-SiO2 and Na2O-Al2O3-SiO2

Infrared (IR) and Raman spectroscopic methods are important complementary techniques in structural studies of aluminosilicate glasses. Both techniques are sensitive to small-scale (<15 Å) structural features that amount to units of several SiO₄ tetrahedra. Application of IR spectroscopy has, however, been limited by the more complex nature of the IR spectrum compared with the Raman spectrum, particularly at higher frequencies (1200–800 cm^?1) where strong antisymmetric Si-O and Si-O-Si absorptions predominate in the former. At lower frequencies, IR spectra contain bands that have substantial contributions from ‘cage-like’ motions of cations in their oxygen co-ordination polyhedra. In aluminosilicates these bands can provide information on the structural environment of Al that is not obtainable directly from Raman studies. A middle frequency envelope centred near 700 cm^?1 is indicative of network-substituted AlO₄ polyhedra in glasses with Al/(Al+Si)>0·25 and a band at 520–620cm^?1 is shown to be associated with AlO₆ polyhedra in both crystals and glasses. The IR spectra of melilite and melilite-analogue glasses and crystals show various degrees of band localization that correlate with the extent of Al, Si tetrahedral site ordering. An important conclusion is that differences in Al, Si ordering may lead to very different vibrational spectra in crystals and glasses of otherwise gross chemical similarity.     

A Raman spectroscopic study of H/D isotopically substituted hydrous aluminosilicate glasses

We have obtained high quality Raman spectra for two H/D isotopically substituted hydrous aluminosilicate glasses with compositions along the NaAlSi₃O₈-SiO₂ join. Consistent with the results of previous studies, the isotope shift for the band near 900 cm^–1, whose intensity grows with increasing water content, is extremely small: v _h /v _d = 1.004 ± 0.004. The lack of a definite H/D isotope shift for this band does not, however, preclude its association with a vibration of a hydrous species in the glass, because of likely strong coupling between different vibrational modes of hydrated framework species. The 900 cm^–1 band could well be due to a T — OH (T = Si, Al) stretching or bending vibration in the hydrous glass, as required by the presence of a combination band near 4500 cm^–1 in near-infrared spectra.     

Molecular orbital calculations of vibrations in three-membered aluminosilicate rings

Ab initio, molecular orbital calculations at the 3–21G^* level were carried out on H₆Si₃O₉, [H₆Si₂AlO₂]^1?, [H₆SiAl₂O₉]^2?, and [H₆A1₃O₉]^3? cyclic molecules in order to determine their structures and vibrational frequencies. These three-membered rings were found to have minima in their potential energy surfaces indicating stability of the species. The H₆Si₃O₉ ring was found to be slightly non-planar, but the [H₆SiAl₂O₉]^2? and [H₆Al₃3O₉]^3? configurations are more planar. Vibrational frequencies of the Raman-active, bridging oxygen “breathing” modes increase with Si⁴⁺ content. Galeener's (1982a, b) assignment of the D₂ peak (606 cm^?1) in the Raman spectrum of vitreous silica to an oxygen breathing mode in rings of three SiO₄ tetrahedra is reconfirmed. Correlation of the ring breathing mode frequencies as a function of (AI/AI + Si) with Raman peaks in the SiO₂-NaAlSiO₄ system is high. Three-membered aluminosilicate rings are likely to exist and give rise to Raman peaks between 540 and 600 cm_?1 in fully-polymerized aluminosilicate glasses.     

A Raman spectroscopic study of glasses along the joins silica-calcium aluminate,silica-sodium aluminate,and silica-potassium aluminate

Aluminosilicate glasses with compositions along the joins silica-calcium aluminate, silica sodium aluminate and silica-potassium aluminate have been prepared by conventional and solar melting techniques and studied by Raman spectroscopy. The Raman spectra of crystalline calcium aluminate, anorthite and silica polymorphs are discussed in relation to their crystal structures, and compared with the spectra of the corresponding glasses. The glass and crystal spectra are generally comparable, suggesting similar vibrational structures. These crystals have structures based on tetrahedral aluminosilicate frameworks, and a similar molecular structure is suggested for the glasses, although it is noted that the Raman spectra do not directly characterize the aluminate polyhedra. Within the three glass series, our interpretation of the unresolved high-frequency bands shows the appearance of discrete bands near 1120, 1000, 930 and 890 cm^?1 as the silica content is decreased. This is compared with the behaviour of high-frequency bands in simple silicate systems, and used to suggest that the four bands in the aluminosilicate systems are due to stretching vibrations of silicate tetrahedra bound to one, two, three and four aluminium atoms. The spectra of calcium, sodium, potassium and lithium aluminosilicate glasses with similar silica contents are compared, and interpreted by the above model. This is used to construct a simple model for the effect of metal cation on aluminosilicate molecular groups in the glass structure, consistent with the results of calorimetric studies on similar systems.     

Solubility mechanisms of fluorine in peralkaline and meta-aluminous silicate glasses and in melts to magmatic temperatures

Structural interaction between dissolved fluorine and silicate glass (25°C) and melt (to 1400°C) has been examined with ¹⁹F and ²⁹Si MAS NMR and with Raman spectroscopy in the system Na₂O-Al₂O₃-SiO₂ as a function of Al₂O₃ content. Approximately 3 mol.% F calculated as NaF dissolved in these glasses and melts. From ¹⁹F NMR spectroscopy, four different fluoride complexes were identified. These are (1) Na-F complexes (NF), (2) Na-Al-F complexes with Al in 4-fold coordination (NAF), (3) Na-Al-F complexes with Al in 6-fold coordination with F (CF), and (4) Al-F complexes with Al in 6-fold, and possibly also 4-fold coordination (TF). The latter three types of complexes may be linked to the aluminosilicate network via Al-O-Si bridges.The abundance of sodium fluoride complexes (NF) decreases with increasing Al/(Al + Si) of the glasses and melts. The NF complexes were not detected in meta-aluminosilicate glasses and melts. The NAF, CF, and TF complexes coexist in peralkaline and meta-aluminosilicate glasses and melts.From ²⁹Si-NMR spectra of glasses and Raman spectra of glasses and melts, the silicate structure of Al-free and Al-poor compositions becomes polymerized by dissolution of F because NF complexes scavenge network-modifying Na from the silicate. Solution of F in Al-rich peralkaline and meta-aluminous glasses and melts results in Al-F bonding and aluminosilicate depolymerization.Temperature (above that of the glass transition) affects the Qⁿ-speciation reaction in the melts, 2Q³ ⇔ Q⁴ + Q², in a manner similar to other alkali silicate and alkali aluminosilicate melts. Dissolved F at the concentration level used in this study does not affect the temperature-dependence of this speciation reaction.     

Phosphorus solubility mechanisms in haplogranitic aluminosilicate glass and melt: effect of temperature and aluminum content

The solubility behavior of phosphorus in glasses and melts in the system Na₂O-Al₂O₃-SiO₂-P₂O₅ has been examined as a function of temperature and Al₂O₃ content with microRaman spectroscopy. The Al₂O₃ was added (2, 4, 5, 6, and 8 mol% Al₂O₃) to melts with 80 mol% SiO₂ and ∼2 mol% P₂O₅. The compositions range from peralkaline, via meta-aluminous to peraluminous. Raman spectra were obtained of both the phosphorus-free and phosphorous-bearing glasses and melts between 25 and 1218 °C. The Raman spectrum of Al-free, P-bearing glass exhibits a characteristic strong band near 940 cm⁻¹ assigned to P=O stretching in orthophosphate complexes together with a weaker band near 1000 cm⁻¹ assigned P₂O₇ complexes. With increasing Al content, the proportion of P₂O₇ initially increases relative to PO₄ and is joined by AlPO₄ complexes which exhibit a characteristic P-O stretch mode slightly above 1100 cm⁻¹. The latter complex appears to dominate in meta-aluminosilicate glass and is the only phosphate complex in peraluminous glasses. When P-bearing peralkaline silicate and aluminosilicate glasses are transformed to supercooled melts, there is a rapid decrease in PO₄/P₂O₇ so that in the molten state, PO₄ units are barely discernible. The P₂O₇/AlPO₄ abundance ratio in peralkaline compositions increases with increasing temperature. This decrease in PO₄/P₂O₇ with increasing temperature results in depolymerization of the silicate melts. Dissolved P₂O₅ in peraluminous glass and melts forms AlPO₄ complexes only. This solution mechanism has no discernible influence on the aluminosilicate melt structure. There is no effect of temperature on this solution mechanism. Received: 7 October 1997 / Accepted: 11 May 1998     

Spectroscopic analysis (FTIR, Raman) of water in mafic and intermediate glasses and glass inclusions

Micro-Raman spectroscopy, even though a very promising technique, is not still routinely applied to analyse H₂O in silicate glasses. The accuracy of Raman water determinations critically depends on the capability to predict and take into account both the matrix effects (bulk glass composition) and the analytical conditions on band intensities. On the other hand, micro-Fourier transform infrared spectroscopy is commonly used to measure the hydrous absorbing species (e.g., hydroxyl OH⁻ and molecular H₂O) in natural glasses, but requires critical assumptions for the study of crystal-hosted glasses. Here, we quantify for the first time the matrix effect of Raman external calibration procedures for the quantification of the total H₂O content (H₂O_T = OH⁻ + H₂O_m) in natural silicate glasses. The procedures are based on the calibration of either the absolute (external calibration) or scaled (parameterisation) intensity of the 3550 cm⁻¹ band. A total of 67 mafic (basanite, basalt) and intermediate (andesite) glasses hosted in olivines, having between 0.2 and 4.8 wt% of H₂O, was analysed. Our new dataset demonstrates, for given water content, the height (intensity) of Raman H₂O_T band depends on glass density, reflectance and water environment. Hence this matrix effect must be considered in the quantification of H₂O by Raman spectroscopy irrespective of the procedure, whereas the parameterisation mainly helps to predict and verify the self-consistency of the Raman results. In addition, to validate the capability of the micro-Raman to accurately determine the H₂O content of multicomponent aluminosilicate glasses, a subset of 23 glasses was analysed by both micro-Raman and micro-FTIR spectroscopy using the band at 3550 cm⁻¹. We provide new FTIR absorptivity coefficients (ε₃₅₅₀) for basalt (62.80 ± 0.8 L mol⁻¹ cm⁻¹) and basanite (43.96 ± 0.6 L mol⁻¹ cm⁻¹). These values, together with an exhaustive review of literature data, confirm the non-linear decline of the FTIR absorptivity coefficient (ε₃₅₅₀) as the glass depolymerisation increases. We demonstrate the good agreement between micro-FTIR and micro-Raman determination of H₂O in silicate glasses when the matrix effects are properly considered.     

Structure and cation disorder of hydrous ringwoodite, γ-Mg1.89Si0.98H0.30O4

The structure of a single crystal hydrous ringwoodite, Mg_1.89Si_0.98H_0.30O₄ synthesized at conditions of 1300?°C and 20?GPa has been analyzed. Crystallographic data for hydrous ringwoodite obtained are; Cubic with Space group: Fd3m (no. 227). a= 8.0693(5)?Å, V=526.41(9)?ų, Z=8, D_calc= 3.48?g?cm^?3. The results of site occupancy refinement using higher angle reflections showed the existence of a small degree of Mg²⁺-Si⁴⁺ disorder in the structure such as (Mg_1.84Si_0.05□_0.11)(Si_0.93Mg_0.05□_0.02)H_0.30O₄. The IR and Raman spectra were measured and OH vibration spectra were observed. A broad absorption band was observed in the IR spectrum and the maxima were observed at 3160?cm^?1 in the IR and at 3165?cm^?1 and 3685?cm^?1 in relatively sharp Raman spectra, which suggest that locations between O-O pairs around the octahedral 16c and 16d sites are possible sites for hydrogen.     

Quantification of water content and speciation in natural silicic glasses (phonolite, dacite, rhyolite) by confocal microRaman spectrometry

The determination of total water content (H₂O_T: 0.1-10 wt%) and water speciation (H₂O_molecular/OH) in volcanic products by confocal microRaman spectrometry are discussed for alkaline (phonolite) and calcalkaline (dacite and rhyolite) silicic glasses. Shape and spectral distribution of the total water band (H₂O_T) at ∼3550 cm⁻¹ show systematic evolution with glass H₂O_T, water speciation and NBO/T. In the studied set of silicic samples, calibrations based on internal normalization of the H₂O_T band to a band related to vibration of aluminosilicate network (TOT) at ∼490 cm⁻¹ vary with glass peraluminosity. An external calibration procedure using well-characterized glass standards is less composition-dependent and provides excellent linear correlation between total dissolved water content and height or area of the H₂O_T Raman band. Accuracy of deconvolution procedure of the H₂O_T band to quantify water speciation in water-rich and depolymerized glasses depends on the strength of OH hydrogen bonding. System confocal performance, scattering from embedding medium and glass microcrystallinity have a crucial influence on accuracy of Raman analyses of water content in glass-bearing rocks and melt inclusions in crystals.     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Vibrational interactions of tetrahedra in silicate glasses and crystals

Normal coordinate calculations have been carried out on partially polymerized simple silicate crystals, including Li and Na di- and metasilicates, Li and Gd pyrosilicates, thortveitite and rankinite. In the antisymmetric Si-O stretching modes which are active at 800–1200 cm^?1 in infrared spectra, Si-Obr vibrations occur at higher frequencies than Si-Onb vibrations if the bonds have equivalent strengths. However, this relationship is usually reversed when bridging oxygens are overbonded and non-bridging oxygens are underbonded in terms of Pauling bond strengths, a situation which is generally more common in crystals. An observed bimodality of the high-frequency envelope in infrared spectra of glasses in the alkali oxide-silica systems may be somewhat fortuitous, with the high frequency component (ca. 1100 cm^?1) representing underbonded non-bridging oxygens and saturated bridging oxygens, and the lower-frequency component (ca. 1000 cm^?1) mainly oversaturated bridging oxygens. Significant differences between crystals and glasses in the number and location of the main high-frequency infrared peaks suggest that there are short-range bonding rearrangements in the glasses, and that crystallite models are not applicable. Mid-frequency (600–800 cm^?1) infrared modes in silicates more polymerized than the pyrosilicate (Si₂O₇) appear to be mostly antisymmetric modes in which Si rattles against bridging oxygens, rather than symmetric stretching modes.     

23Na NMR chemical shifts and local Na coordination environments in silicate crystals,melts and glasses

In order to decipher information about the local coordination environments of Na in anhydrous silicates from ²³Na nuclear magnetic resonance spectroscopy (NMR), we have collected ²³Na magic angle spinning (MAS) NMR spectra on several sodium-bearing silicate and aluminosilicate crystals with known structures. These data, together with those from the literature, suggest that the ²³Na isotropic chemical shift correlates well with both the Na coordination and the degree of polymerization (characterized by NBO/T) of the material. The presence of a dissimilar network modifier also affects the ²³Na isotropic chemical shift. From these relations, we found that the average Na coordinations in sodium silicate and aluminosilicate liquids of a range of compositions at 1 bar are nearly constant at around 6–7. The average Na coordinations in glasses of similar compositions also vary little with Na content (degree of polymerization). However, limited data on ternary alkali silicate and aluminosilicate glasses seem to suggest that the introduction of another network-modifier, such as K or Cs, does cause variations in the average local Na coordination. Thus it appears that the average Na coordination environments in silicate glasses are more sensitive to the presence of other network-modifiers than to the variations in the topology of the silicate tetrahedral network. Further studies on silicate glasses containing mixed cations are necessary to confirm this conclusion.     

Aluminum speciation, vibrational entropy and short-range order in calcium aluminosilicate glasses

The heat capacity and vibrational entropy of a calcium aluminate and three peraluminous calcium aluminosilicate glasses have been determined from 2 to 300 K by heat-pulse relaxation calorimetry. Together with previous adiabatic data for six other glasses in the system CaO-Al₂O₃-SiO₂, these results have been used to determine partial molar heat capacities and entropies for five species namely, SiO₂, CaO and three different sorts of Al₂O₃ in which Al is 4-, 5- and 6-fold coordinated by oxygen. Given the determining role of oxygen coordination on low-temperature heat capacity, the composition independent entropies found for SiO₂ and CaO indicate that short-range order around Si and Ca is not sensitive to aluminum speciation up to the highest fraction of 25% observed for ^VAl by NMR spectroscopy. Because of the higher room-temperature vibrational entropy of ^IVAl₂O₃ (72.8 J/mol K) compared to ^VAl₂O₃ (48.5 J/mol K), temperature-induced changes from ^IVAl to ^VAl give rise to a small negative contribution of the order of 1 J/mol K to the partial molar configurational heat capacity of Al₂O₃ in melts. Near 0 K, pure SiO₂ glass distinguishes itself by the importance of the calorimetric boson peak. On a g atom basis, the maximum of this peak varies with the composition of calcium aluminosilicate glasses by a factor of about 2. It does not show smooth variations, however, either as a function of SiO₂ content, at constant CaO/Al₂O₃ ratio, or as a function of Al₂O₃ content, at constant SiO₂ content.     

Phase transitions in langbeinites II: Raman spectroscopic investigations of K2Cd2(SO4)3

Polarized single crystal Raman spectra of the langbeinite K₂Cd₂(SO₄)₃ were recorded for different polarisations. With a view to understanding the phase transition mechanism, the lattice vibrational spectra (0–300 cm^?1), as well as the SO₄ symmetric stretching mode v ₁ (1,022 cm^?1), were recorded at different temperatures. No soft modes were observed. From the study of the temperature variation of the integrated intensity I ₀ and band width Γ of the hard mode (1,022 cm^?1), both SO₄ libration and SO₄ order/disorder models were ruled out as possible phase transition models. On the other hand, the model of Speer and Salje (paper I), involving the distortion of the polyhedra around Cd and K ions, explains the observed temperature behaviour of the Raman spectra very well. The consequences of a possible hypothetical high-temperature phase are discussed.     

Ab initio calculation of H, O, Al and Si NMR parameters, vibrational frequencies and bonding energetics in hydrous silica and Na-aluminosilicate glasses

Ab initio, molecular orbital (MO) calculations were performed on model systems of SiO₂, NaAlSi₃O₈ (albite), H₂O-SiO₂ and H₂O-NaAlSi₃O₈ glasses. Model nuclear magnetic resonance (NMR) isotropic chemical shifts (δ_iso) for ¹H, ¹⁷O, ²⁷Al and ²⁹Si are consistent with experimental data for the SiO₂, NaAlSi₃O₈, H₂O-SiO₂ systems where structural interpretations of the NMR peak assignments are accepted. For H₂O-NaSi₃AlO₈ glass, controversy has surrounded the interpretation of NMR and infrared (IR) spectra. Calculated δ_iso¹H, δ_iso¹⁷O, δ_iso²⁷Al and δ_iso²⁹Si are consistent with the interpretation of Kohn et al. (1992) that Si-(OH)-Al linkages are responsible for the observed peaks in hydrous Na-aluminosilicate glasses. In addition, a theoretical vibrational frequency associated with the Kohn et al. (1992) model agrees well with the observed shoulder near 900 cm⁻¹ in the IR and Raman spectra of hydrous albite glasses. MO calculations suggest that breaking this Si-(OH)-Al linkage requires ∼+56 to +82 kJ/mol which is comparable to the activation energies for viscous flow in hydrous aluminosilicate melts.     

Water solubility mechanism in hydrous aluminosilicate glasses: information from Al MAS and MQMAS NMR

New ²⁷Al NMR data are presented in order to clarify the discrepancies in the interpretation of the previous ²⁷Al Magic Angle Spinning (MAS) spectra from hydrous aluminosilicate glasses. The ²⁷Al MAS data have been collected at much higher magnetic field (14.1 and 17.6 T) than hitherto, and in addition, multiple quantum (MQ) MAS NMR data are presented for dry and hydrous nepheline glasses and NaAlSi_7.7O_17.4 glass that, according to the model of Zeng et al. (Zeng Q., Nekvasil H., and Grey C. P. 2000. In support of a depolymerisation model for water in sodium aluminosilicate glasses: Information from NMR spectroscopy. Geochim. Cosmochim. Acta64, 883-896), should produce a high fraction (up to 30%) of Al in Al Q³-OH on hydration. Although small differences in the MAS spectra of anhydrous and hydrous nepheline glasses are observed, there is no evidence for the existence of significant (>∼2%) amounts of Q³ Al-OH in these glasses in either the MAS or MQMAS data.     

Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts

Configurational changes with temperature are important for the thermodynamic and transport properties of most aluminosilicate melts, but in general are not well understood. Here, we present high-resolution ²⁷Al and ¹⁷O NMR data on several calcium aluminosilicate glasses prepared with varying quench rates and thus with fictive temperatures that span ranges up to about 200 K. In all compositions the content of five-coordinated aluminum increases with fictive temperature, in agreement with recent high temperature NMR data on melts. In a glass of CaAl₂Si₂O₈ (“anorthite”) composition, the content of non-bridging oxygens also increases with temperature; however this effect was not observed in a sample with a much higher CaO/Al₂O₃ ratio. We present a consistent notation for reactions among structural species in these systems that clarify why in some cases, high-coordinated network cations may appear on the same side of the reaction, while in others they occur on the opposite sides: the key difference is in accounting for all coordination changes for oxygens. Mixing of non-bridging oxygens and of high-coordinated aluminum make significant contributions to the overall configurational entropy and heat capacity of the melts, as does the mixing of various bridging oxygens and of tetrahedral network cations. Other, less well known, types of increase in disorder with temperature may be important as well.     

Cation field strength effects on high pressure aluminosilicate glass structure: Multinuclear NMR and La XAFS results

We examined aluminosilicate glasses containing a variety of network modifying to intermediate cations (Li, La, Sc, and Fe), quenched from melts at 1 atm to 8 GPa, to further investigate the role of cation field strength in Al coordination changes and densification. ²⁷Al Nuclear Magnetic Resonance Spectroscopy (NMR) reveals that the mean Al coordination increases with increasing pressure in the Li-containing glasses, which can be explained by a linear dependence of fractional change in Al coordination number on cation field strengths in similar K-, Na-, and Ca-containing aluminosilicate glasses (K < Na < Li < Ca). Measured recovered densities follow a similar linear trend. In contrast, the La-containing glasses have significantly lower mean Al coordination numbers at given pressures than the cation field strength of La and glass density would predict. La L₃ X-ray absorption fine structure (XAFS) spectroscopy results indicate a significant increase with pressure in average La-O bond distances, suggesting that La and Al may be “competing” for higher coordinated sites and hence that both play a significant role in the densification of these glasses, especially in the lower pressure range. However, in Na aluminosilicate glasses with small amounts of Sc, ⁴⁵Sc NMR reveals only modest Sc coordination changes, which do not seem to significantly affect the mean Al coordination values. For a Li aluminosilicate glass, ¹⁷O MAS and multiple quantum magic angle spinning (3QMAS) NMR data are consistent with generation of more highly coordinated Al at the expense of non-bridging oxygen (NBO), whereas La aluminosilicate glasses have roughly constant O environments, even up to 8 GPa. Finally, we demonstrate that useful ²³Na and ²⁷Al MAS NMR spectra can be collected for Ca-Na aluminosilicate glasses containing up to 5 wt.% Fe oxide. We discuss the types of structural changes that may accompany density increases with pressure and how these structural changes are affected by the presence of different cations.     

Oxygen sites in hydrous aluminosilicate glasses: the role of Al-O-Al and H2O

We describe here high-field ¹⁷O magic-angle-spinning (MAS) and triple-quantum MAS (3QMAS) NMR spectra for several alkali silicate and Na, K, and Ca aluminosilicate glasses containing up to 10 wt.% water. The H₂O site appears to have a large quadrupolar coupling constant, and its chemical shift increases from Na- to K- glasses, suggesting significant cation-H₂O interactions. In ¹⁷O one-pulse MAS and 3QMAS and ²⁷Al one-pulse NMR experiments, major differences were seen between spectra for anhydrous and hydrous calcium aluminosilicate glasses. The changes in the ¹⁷O MAS spectra can be explained by the addition of an H₂O peak and to the disappearance of an Al-O-Al peak from the ¹⁷O NMR spectrum for the hydrous glass. The ²⁷Al results are consistent with this interpretation.