Insight into sodium silicate glass structural organization by multinuclear NMR combined with first-principles calculations

Short and medium range order of silica and sodium silicate glasses have been investigated from a quantitative analysis of ²⁹Si MAS NMR and ²³Na, ¹⁷O MQMAS NMR spectra. The method described enables the extraction of the underlying ¹⁷O NMR parameter distributions of bridging oxygens (BOs) and non-bridging oxygens (NBOs), and yields site populations which are confirmed by ²⁹Si NMR data. The extracted NMR parameter distributions and their variations with respect to the glass chemical composition can then be analyzed in terms of local structural features (bond angles and bond lengths, coordination numbers) with the help of molecular dynamics simulations combined with first-principles calculations of NMR parameters. Correlations of relevant structural parameters with ²³Na, ²⁹Si and ¹⁷O NMR interactions (isotropic chemical shift δ_iso, quadrupolar coupling constant C_Q and quadrupolar asymmetry parameter η_Q) are re-examined and their applicability is discussed. These data offer better insights into the structural organization of the glass network, including both chemical and topological disorder. Adding sodium to pure silica significantly diminishes the Si-O-Si bond angles and leads to a longer mean Si-O bond length with a slight decrease of the mean Na-O bond length. Moreover, the present data are in favor of a homogeneous distribution of Na around both oxygen species in the silicate network. Finally, our approach was found to be sensitive enough to investigate the effect of addition of a small quantity of molybdenum oxide (about 1 mol%) on the ¹⁷O MAS spectrum, opening new possibilities for investigating the Mo environment in silicate glasses.     

Structure of hydrous aluminosilicate glasses along the diopside-anorthite join: A comprehensive one- and two-dimensional H and Al NMR study

We have taken a systematic approach utilizing advanced solid-state NMR techniques to gain new insights into the controversial issue concerning the dissolution mechanisms of water in aluminosilicate melts (glasses). A series of quenched anhydrous and hydrous (∼2 wt% H₂O) glass samples along the diopside (Di, CaMgSi₂O₆)—anorthite (An, CaAl₂Si₂O₈) join with varying An components (0, 20, 38, 60, 80, and 100 mol %) have been studied. A variety of NMR techniques, including one-dimensional (1D) ¹H and ²⁷Al MAS NMR, and ²⁷Al → ¹H cross-polarization (CP) MAS NMR, as well as two-dimensional (2D) ¹H double-quantum (DQ) MAS NMR, ²⁷Al triple-quantum (3Q) MAS NMR, and ²⁷Al → ¹H heteronuclear correlation NMR (HETCOR) and 3QMAS/HETCOR NMR, have been applied. These data revealed the presence of SiOH, free OH ((Ca,Mg)OH) and AlOH species in the hydrous glasses, with the last mostly interconnected with Si and residing in the more polymerized parts of the structure. Thus, there are no fundamental differences in water dissolution mechanisms for Al-free and Al-bearing silicate melts (glasses), both involving two competing processes: the formation of SiOH/AlOH that is accompanied by the depolymerization of the network structure, and the formation of free OH that has an opposite effect. The latter is more important for depolymerized compositions corresponding to mafic and ultramafic magmas.Aluminum is dominantly present in four coordination (Al^IV), but a small amount of five-coordinate Al (Al^V) is also observed in all the anhydrous and hydrous glasses. Furthermore, six-coordinate Al (Al^VI) is also present in most of the hydrous glasses. As Al of higher coordinations are favored by high pressure, Al^VIOH and Al^VOH may become major water species at higher pressures corresponding to those of the Earth’s mantle.     

Structure vs. composition: A solid-state H and Si NMR study of quenched glasses along the Na2O-SiO2-H2O join

A suite of six hydrous (7 wt.% H₂O) sodium silicate glasses spanning sodium octasilicate to sodium disilicate in composition were analyzed using ²⁹Si single pulse (SP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, ¹H-²⁹Si cross polarization (CP) MAS NMR, and fast MAS ¹H-NMR. From the ²⁹Si SPMAS data it is observed that at low sodium compositions dissolved water significantly depolymerizes the silicate network. At higher sodium contents, however, dissolved H₂O does not affect a significant increase in depolymerization over that predicted based on the Na/Si ratio alone. The fast MAS ¹H-NMR data reveal considerable complexity in proton environments in each of the glasses studied. The fast MAS ¹H-NMR spectra of the highest sodium concentration glasses do not exhibit evidence of signficantly greater fractions of dissolved water as molecular H₂O than the lower sodium concentration glasses requiring that the decrease in polymerization at high sodium contents involves a change in sodium solution mechanism. Variable contact time ¹H-²⁹Si cross polarization (CP) MAS NMR data reveal an increase in the rotating frame spin lattice relaxation rate constant (T_1ρ*) for various Qⁿ species with increasing sodium content that correlates with a reduction in the average ¹H-²⁹Si coupling strength. At the highest sodium concentration, however, T_1ρ* drops significantly, consistent with a change in the Na₂O solution mechanism.     

Solution mechanisms of H2O in depolymerized peralkaline melts

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—V. The polymeric structure of silica in albite and anorthite composition glass and the devitrification of amorphous anorthite

²⁹Si MAS NMR experiments have been carried out to determine the silica species distribution (Q distribution) in albite, NaAlSi₃O₈, and anorthite, CaAl₂Si₂O₈, composition glasses (designated albite and anorthite glass). Our results indicate that the Q distribution of albite glass contains all five possible silica species and shows a tendency towards high Q₃ and Q₄ concentrations, whereas anorthite glass does not contain Q₄ and has a high Q₀ concentration. Rationalizations are made in terms of the observed Q distributions to explain differences in devitrification behavior of these two glasses. ²⁷Al MAS NMR data for these glasses suggest that differences in devitrification behavior between these two glasses should be ascribed to small growth rates rather than small nucleation rates of crystalline albite from albite glass.     

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.     

A theoretical interpretation of the chemical shift of Si NMR peaks in alkali borosilicate glasses

In ²⁹Si-NMR, it has so far been accepted that the chemical shifts of Qⁿ species (SiO₄ units containing n bridging oxygens) were equivalent between alkali borosilicate and boron-free alkali silicate glasses. In the sodium borosilicate glasses with low sodium content, however, a contradiction was confirmed in the estimation of alkali distribution; ¹¹B NMR suggested that Na ions were entirely distributed to borate groups to form BO₄ units, whereas a −90 ppm component was also observed in ²⁹Si-NMR spectra, which has been attributed to Q³ species associated with a nonbridging oxygen (NBO). Then, cluster molecular orbital calculations were performed to interpret the −90 ppm component in the borosilicate glasses. It was found that a silicon atom which had two tetrahedral borons (B4) as its second nearest neighbors was similar in atomic charge and Si2p energy to the Q³ species in boron-free alkali silicates. Unequal distribution of electrons in Si-O-B4 bridging bonds was also found, where much electrons were localized on the Si-O bonds. It was finally concluded that the Si-O-B4 bridges with narrow bond angle were responsible for the −90 ppm ²⁹Si component in the borosilicate glasses. There still remained another interpretation; the Q³ species were actually present in the glasses, and NBOs in the Q³ species were derived from the tricluster groups, such as (O₃Si)O(BO₃)₂. In the glasses with low sodium content, however, it was concluded that the tricluster groups were not so abundant to contribute to the −90 ppm component.     

Water dissolution in albite melts:: Constraints from ab initio NMR calculations

Hartree-Fock and B3LYP NMR calculations were performed at the 6-311+G(2df,p) level on cluster models representing albite glasses using B3LYP/6 to 31G* optimized geometries. Calculation results on several well-known crystalline materials, such as low albite and KHSi₂O_5, were used to check the accuracy of the calculation methods.Calculated ²⁹Si-NMR results on clusters that model protonation of Al-O-Si linkages and the replacement of Na⁺ by H⁺ indicate a major increase in Si-O(H) bond length and a 5 ppm difference in δ_iso for ²⁹Si compared to that for anhydrous albite glass. The calculated δ_iso of ²⁷Al in such linkages agrees with the experimental data, but shows an increase in C_q that cannot be fully diminished by H-bonding to additional water molecules. This protonation model is consistent with both experimental ¹⁷O NMR data and the major peak of ¹H-NMR spectra. It cannot readily explain the existence of the small peak in the experimental ¹H spectra around 1.5 ppm. Production of the depolymerized units Al [Q³]-O-H upon the dissolution of water is not consistent with ²⁷Al, ¹H, or ¹⁷O NMR experimental results. Production of Si [Q³]-O-H is consistent with all of the experimental ¹⁷O and ¹H-NMR data; such units can produce both the major peak at 3.5 ppm and the small peak at 1.5 ppm in ¹H spectra, either with or without hydrogen bonding. This species, however, cannot produce the main features of ²⁹Si spectra.It is concluded that although neither protonation nor the production of Si [Q³]-O-H alone is consistent with the available experimental data, the combination of these two processes is consistent with available experimental NMR data.     

The distribution of sodium ions in aluminosilicate glasses: a high-field Na-23 MAS and 3Q MAS NMR study

The local configurations around sodium ions in silicate glasses and melts and their distributions have strong implications for the dynamic and static properties of melts and thus may play important roles in magmatic processes. The quantification of distributions among charge-balancing cations, including Na⁺ in aluminosilicate glasses and melts, however, remains a difficult problem that is relevant to high-temperature geochemistry as well as glass science.Here, we explore the local environment around Na⁺ in charge-balanced aluminosilicate glasses (the NaAlO₂-SiO₂ join) and its distribution using ²³Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy at varying magnetic fields of 9.4, 14.1, and 18.8 T, as well as triple-quantum (3Q)MAS NMR spectroscopy at 9.4 T, to achieve better understanding of the extent of disorder around this cation. We quantify the extent of this disorder in terms of changes in Na-O distance (d[Na-O]) distributions with composition and present a structural model favoring a somewhat ordered Na distribution, called a “perturbed” Na distribution model. The peak position in ²³Na MAS spectra of aluminosilicate glasses moves toward lower frequencies with increasing Si/Al ratios, implying that the average d(Na-O) increases with increasing R. The peak width is significantly reduced at higher fields (14.1 and 18.8 T) because of the reduced effect of second-order quadrupolar interaction, and ²³Na MAS NMR spectra thus provide relatively directly the Na chemical shift distribution and changes in atomic environment with composition. Chemical shift distributions obtained from ²³Na 3Q MAS spectra are consistent with MAS NMR data, in which deshielding decreases with R. The average distances between Na and the three types of bridging oxygens (BOs) (Na-{Al-O-Al}, Na-{Si-O-Al}, and Na-{Si-O-Si}) were obtained from the correlation between d(Na-O) and isotropic chemical shift. The calculated d(Na-{Al-O-Al}) of 2.52 Å is shorter than the d(Na-{Si-O-Si}) of 2.81 Å, and d(Na-{Al-O-Al}) shows a much narrower distribution than the other types of BOs. ²³Na chemical shifts in binary (Al-free) sodium silicate glasses are more deshielded and have ranges distinct from those of aluminosilicate glasses, implying that d(Na-NBO) (nonbridging oxygen) is shorter than d(Na-BO) and that d(Na-{Si-O-Si}) in binary silicates can be shorter than that in aluminosilicate glasses. The results given here demonstrate that high-field ²³Na NMR is an effective probe of the Na⁺ environment, providing not only average structural information but also chemically and topologically distinct chemical shift ranges (distributions) and their variation with composition and their effects on static and dynamic properties.     

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative ¹⁹F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q³ groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the “Icelandic” samples and with duration of field weathering for both “Icelandic” and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q³ sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily monitored by quantitative ¹⁹F solid-state NMR, therefore provides a chemically specific and quantifiable proxy to understand the nature of how sites on dissolving silicates control dissolution. Furthermore, ²⁷Al NMR techniques are shown here to be useful in identifying clays on the glass surfaces, and these methods are therefore effective for quantifying concentrations of weathering impurities. Our interpretations offer a testable hypothesis for the mechanism of proton-promoted dissolution for low-iron aluminosilicate minerals and glasses and suggest that future investigations of reactive surfaces with high-sensitivity NMR techniques are warranted.     

Quantum mechanical calculation of 23Na NMR shieldings in silicates and aluminosilicates

To assist in the assignment and interpretation of ²³Na NMR spectra in silicate and aluminosilicate minerals and glasses we have calculated the ²³Na NMR shieldings and the electric field gradients (EFG) at the Na for a number of Na-containing species. Included are Na(OH₂) _n ⁺, n = 1, 2, 4, 5, 6 and 8, and Na⁺ complexes with SiH₃OH, SiH₃ONa and O(SiH₃)₂. We have also evaluated shieldings and EFGs for Na-centered clusters extracted from crystalline Na₂SiO₃ and anhydrous sodalite, Na₆[AlSiO₄]₆. Using 6-31G* SCF optimized geometries and the GIAO method with a 6-31G* basis set [and 6-311(2d,p) bases for the smaller clusters] we find a calculated increase in shielding with coordination number (CN) for the Na(OH₂) _n ⁺, n = 4, 6, 8 series that agrees reasonably well with experimental trends. Calculated changes in the Na shielding as water is replaced by bridging or nonbridging silicate O atoms are also consistent with experimental observations. The deshielding of Na (with respect to gas-phase Na⁺) which is produced by an O-containing ligand is a strongly decreasing function of the R(Na–O) and a weakly decreasing function of the underbonding or free valence of the O. Deshielding contributions to the isotropic shielding from different ligands are additive to good approximation for low CN species, so that the total deshielding can be calculated accurately by summing the contributions from the individual ligands. However for the larger CN species the directly calculated deshieldings are substantially smaller than those obtained using such an additivity approximation. We further test this approximation by calculating the deshieldings for Na in 12 different sites in silicate and aluminosilicate minerals which have recently been studied experimentally, using our calculated deshielding contributions for individual O-containing ligands and experimental values for the Na–O distances. Correlation coefficients between the experimental shifts and the calculated deshieldings are around 0.9 and the slope of the correlation is almost 1.0 . Calculations on large Na-centered clusters extracted from the crystal structures of Na₂SiO₃ and anhydrous sodalite reproduce the experimental values for both NMR shieldings and electric field gradients but at considerable computational cost. Comparison with recent ²³Na NMR studies on hydrous albite glasses indicates that coordination of either H₂O or OH⁻ to the Na could give the magnitude of deshielding observed, depending upon the detailed Na–O distances within the hydrous glass. Received: 31 December 1998 / Revised, accepted: 11 May 1999     

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.     

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.     

Structure of Cl-containing silicate and aluminosilicate glasses: A Cl MAS-NMR study

Chlorine-35 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were collected at 14.1 and 18.8 Tesla fields to determine the atomic scale structural environments of the chloride ions in anhydrous and hydrous silicate and aluminosilicate glasses containing 0.2 to 0.7 wt% Cl. NMR peaks are broad and featureless, but are much narrower than the total chemical shift range for the nuclide in inorganic chlorides. Peak widths are primarily due to quadrupole interactions and to a lesser extent to chemical shift distributions. Peak positions are quite different for the Na- and Ca-containing glasses, suggesting that most Cl⁻ coordination environments contain network modifier cations. Comparison of peak positions and shapes for silicate and aluminosilicate glasses containing either Na or Ca suggests that there is no obvious contribution from Cl⁻ bonded to Al, and relative quantitation of peak areas indicates that there is no systematic undercounting of ³⁵Cl spins in the aluminous vs. the Al-free samples. In Ca-Na silicate glasses with varying Ca/(Ca + Na), the mixed-cation glasses have intermediate chemical shifts between those of the end members, implying that there is not a strong preference of either Ca²⁺ or of Na⁺ around Cl⁻. Hydrous Na-aluminosilicate glasses with H₂O contents up to 5.9 wt% show a shift to higher frequency NMR signal with increasing H₂O content, while the quadrupole coupling constant (C_Q) remains constant at ∼3.3 MHz. However, the change in frequency is much smaller than that expected if H₂O systematically replaced Na⁺ in the first-neighbor coordination shell around Cl⁻. A series of hydrous Ca-aluminosilicate glasses with H₂O contents up to 5.5 wt% show no shift in NMR signal with increasing H₂O content. The C_Q remains constant at ∼4.4 MHz, again suggesting no direct interaction between Cl⁻ and H₂O in these samples.     

The nature of hydroxyl groups in aluminosilicate glasses: Quantifying Si-OH and Al-OH abundances along the SiO2-NaAlSiO4 join by H, Al-H and Si-H NMR spectroscopy

The combined results of ²⁷Al-¹H and ¹H-²⁹Si-¹H cross polarization NMR experiments for hydrous glasses (containing 0.5-2 wt% water) along the SiO₂-NaAlSiO₄ join confirm that the dissolution mechanism of water in aluminosilicate glasses is fundamentally the same as for Al-free systems, i.e. the dissolved water ruptures oxygen bridges and creates Si-OH and Al-OH groups, in addition to forming molecular water (H₂O_mol). The fraction of Al-OH increases non-linearly as the Al content increases with up to half of the OH groups as Al-OH for compositions close to NaAlSiO₄. The relative abundances of the different species are controlled by the degree of Al-avoidance and the relative tendency of hydrolysis of the different types of oxygen bridges, Si-O-Si, Si-O-Al and Al-O-Al. A set of homogeneous reactions is derived to model the measured Al-OH/Si-OH speciation, and the obtained equilibrium constants are in agreement with literature data on the degree of Al-avoidance. With these equilibrium constants, the abundance of the different oxygen species, i.e. Si-O-Si, Si-O-Al, Al-O-Al, Si-OH, Al-OH and H₂O_mol, can be predicted for the entire range of water and Al contents.     

Dissolution mechanisms of water in depolymerized silicate melts: Constraints from H and Si NMR spectroscopy and ab initio calculations

Dissolution of water in magmas significantly affects phase relations and physical properties. To shed new light on the this issue, we have applied ¹H and ²⁹Si nuclear magnetic resonance (NMR) spectroscopic techniques to hydrous silicate glasses (quenched melts) in the CaO-MgO-SiO₂ (CMS), Na₂O-SiO₂, Na₂O-CaO-SiO₂ and Li₂O-SiO₂ systems. We have also carried out ab initio molecular orbital calculations on representative clusters to gain insight into the experimental results.The most prominent result is the identification of a major peak at ∼1.1 to 1.7 ppm in the ¹H MAS NMR spectra for all the hydrous CMS glasses. On the basis of experimental NMR data for crystalline phases and ab initio calculation results, this peak can be unambiguously attributed to (Ca,Mg)OH groups. Such OH groups, like free oxygens, are only linked to metal cations, but not part of the silicate network, and are thus referred to as free hydroxyls in the paper. This represents the first direct evidence for a substantial proportion (∼13∼29%) of the dissolved water as free hydroxyl groups in quenched hydrous silicate melts. We have found that free hydroxyls are favored by (1) more depolymerized melts and (2) network-modifying cations of higher field strength (Z/R²: Z: charge, R: cation-oxygen bond length) in the order Mg > Ca > Na. Their formation is expected to cause an increase in the melt polymerization, contrary to the effect of SiOH formation. The ²⁹Si MAS NMR results are consistent with such an interpretation. This water dissolution mechanism could be particularly important for ultramafic and mafic magmas.The ¹H MAS NMR spectra for glasses of all the studied compositions contain peaks in the 4 to 17 ppm region, attributable to SiOH of a range of strength of hydrogen bonding and molecular H₂O. The relative population of SiOH with strong hydrogen bonding grows with decreasing field strength of the network-modifying cations. Ab initio calculations confirmed that this trend largely reflects hydrogen bonding with nonbridging oxygens.     

Coordination of sodium ions in NaAlO2–SiO2 melts: a high temperature 23Na NMR study

The coordination environment of the sodium ion in the melts of several simple ionic liquids and an Na₂O–Al₂O₃–SiO₂ mixture has been investigated by high temperature ²³Na NMR measurements. A new high temperature NMR probe was utilized for the measurements of the compositional and temperature dependence of the ²³Na NMR chemical shift at temperatures up to 1600?°C. ²³Na NMR spectra of ionic liquids, NaCl, NaBr and NaNO₃, show two peaks at their solid to liquid transition, corresponding to the solid and liquid state, respectively. The ²³Na NMR peak shift in passing from the liquid to the solid is positive. This suggests a decrease in the coordination number for the molten state compared to the crystalline state. The ²³Na peak position for the Na₂O–Al₂O₃–SiO₂ melts of the composition range Na/Al≥1 shifted almost linearly in the positive direction as a function of both the increased degree of depolymerization, NBO/T, and [Al]/([Al]+[Si]). ²³Na MAS-NMR measurement for crystalline silicate compounds of known structure provided a revised relationship between the mean Na–O distances and ²³Na chemical shifts. Comparison of the ²³Na chemical shift of the melts with that of crystalline silicate compounds suggests that the coordination number of Na in those melts is around 6–8 with little compositional dependence. The ²³Na peak position shifted in the negative direction with increasing temperature for sodium silicates, whereas that of aluminosilicates did not show any temperature dependence. The activation energy from the temperature dependence of the ²³Na line width shows little compositional dependence, and the value (51～58?kJ/mol) was close to that of the trace Na ion diffusion in NaAlSi₃O₈ glass.     

Influence of glass composition and alteration solution on leached silicate glass structure: A solid-state NMR investigation

A multinuclear solid-state NMR investigation of the structure of the amorphous alteration products (so called gels) that form during the aqueous alteration of silicate glasses is reported. The studied glass compositions are of increasing complexity, with addition of aluminum, calcium, and zirconium to a sodium borosilicate glass. Two series of gels were obtained, in acidic and in basic solutions, and were analyzed using ¹H, ²⁹Si, and ²⁷Al MAS NMR spectroscopy. Advanced NMR techniques have been employed such as ¹H-²⁹Si and ¹H-²⁷Al cross-polarization (CP) MAS NMR, ¹H double quantum (DQ) MAS NMR and ²⁷Al multiple quantum (MQ) MAS NMR. Under acidic conditions, ²⁹Si CP MAS NMR data show that the repolymerized silicate networks have similar configuration. Zirconium as a second nearest neighbor increases the ²⁹Si isotropic chemical shift. The gel porosity is influenced by the pristine glass composition, modifying the silicon-proton interactions. From ¹H DQ and ¹H-²⁹Si CP MAS NMR experiments, it was possible to discriminate between silanol groups (isolated or not) and physisorbed molecular water near Si (Q²), Si (Q³), and Si (Q⁴) sites, as well as to gain insight into the hydrogen-bonding interaction and the mobility of the proton species. These experiments were also carried out on heated samples (180 °C) to evidence hydrogen bonds between hydroxyl groups on molecular water. Alteration in basic media resulted in a gel structure that is more dependent on the initial glass composition. ²⁷Al MQMAS NMR data revealed an exchange of charge compensating cations of the [AlO₄]⁻ groups during glass alteration. ¹H-²⁷Al CP MAS NMR data provide information about the proximities of these two nuclei and two aluminum environments have been distinguished. The availability of these new structural data should provide a better understanding of the impact of glass composition on the gel structure depending on the nature of the alteration solution.     

The system NaAlSi3O8−H2O−H2 (1200° C, 2 kbar): the solubility and interaction mechanism of fluid species with melt

The H₂O and H₂ solubilities in an albite melt at 1200° C and 2 kbar over the entire range of gas phase composition, from pure hydrogen to pure water were studied in gas-media pressure vessels. The water solubility initially increases with increasing hydrogen content until a maximum of 9.19 wt% H₂O atXH ₂ ^v =0.1 is reached, withXH ₂ ^v >0.1 the water solubility decreases. The hydrogen solubility curve has a maximum atXH ₂ ^v =0.42 where the concentration reaches 0.206 wt% H₂O. Over the entire compositional range¹H NMR (nuclear magnetic resonance) spectra show distinct absorption lines due to protons bound to OH groups and to isolated firmly bound water molecules. In NMR and Raman spectra there were no bands attributable to the H–H vibrations of molecular hydrogen. The X-ray photo-electronic spectra of hydrogen-bearing glasses show the Si2p (99 eV) band which corresponds to the zero-valency silicon. The formation of OH groups and molecular water during interaction between hydrogen-bearing fluids and melts under reducing conditions has a qualitative effect, the same as for water dissolution. Another point of interest is that hydrogen-bearing melts undergo more depolymerization than do hydrous melts.