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1.
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 (T1ρ*) 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, T1ρ* drops significantly, consistent with a change in the Na2O solution mechanism.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
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.  相似文献   

6.
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 (CQ) 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 CQ remains constant at ∼4.4 MHz, again suggesting no direct interaction between Cl− and H2O in these samples.  相似文献   

7.
In order to gain insight into the correlations between 29Si, 17O and 1H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and intertetrahedral (Si-O-Si) angles. These include Si(OH)4 monomers (isolated as well as interacting), Si2O(OH)6 dimers (C2 symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si3O2(OH)8 linear trimers (C2 symmetry) with varying Si-O-Si angles, Si3O3(OH)6 three-membered rings (D3 and C1 symmetries), Si4O4(OH)8 four-membered ring (C4 symmetry) and Si8O12(OH)8 octamer (D4 symmetry). The calculated 29Si, 17O and 1H isotropic chemical shifts (δi Si, δi O and δi H) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated 17O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated 17O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δi Si and the mean Si-O-Si angle for both Q 1 and Q 2, where Q n denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δ i O and the 17O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site symmetry, in addition to the Si-O-Si angle. On the other hand, the 17O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most reliable 17O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the 17O QCC and the 2H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom (Si-O-H···O), and the δ i H increase with the same parameter. Received: 18 July 1997 / Revised, accepted: 23 February 1998  相似文献   

8.
Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report 17O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na2O/SiO2 ratio and Na2O/Al2O3 ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na2O-k(SiO2)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na2O/SiO2 ratio (k), as predicted from the composition. The 17O isotropic chemical shifts (17O δiso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO2 content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO2 content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO2 content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na2O]x[Al2O3]1−xSiO2, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al2O3 content. The variation of oxygen cluster populations suggests that deviation from “Al avoidance” is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity coefficient of silica, would decrease with increasing Al2O3 content at a constant mole fraction of SiO2. Therefore, the activity of silica may decrease from depolymerized binary silicates to fully polymerized sodium aluminosilicate glasses at a constant mole fraction of SiO2.  相似文献   

9.
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)/∂XH2O, 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.  相似文献   

10.
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.  相似文献   

11.
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.  相似文献   

12.
Information about the state of sulfur in silicate melts and glasses is important in both earth sciences and materials sciences. Because of its variety of valence states from S2− (sulfide) to S6+ (sulfate), the speciation of sulfur dissolved in silicate melts and glasses is expected to be highly dependent on the oxygen fugacity. To place new constraint on this issue, we have synthesized sulfur-bearing sodium silicate glasses (quenched melts) from starting materials containing sulfur of different valence states (Na2SO4, Na2SO3, Na2S2O3 and native S) using an internally heated gas pressure vessel, and have applied electron-induced SKα X-ray fluorescence, micro-Raman and NMR spectroscopic techniques to probe their structure. The wavelength shift of SKα X-rays revealed that the differences in the valence state of sulfur in the starting compounds are largely retained in the synthesized sulfur-bearing glasses, with a small reduction for more oxidized samples. The 29Si MAS NMR spectra of all the glasses contain no peaks attributable to the SiO4-nSn (with n > 0) linkages. The Raman spectra are consistent with the coexistence of sodium sulfate (Na2SO4) species and one or more types of more reduced sulfur species containing S-S linkages in all the sulfur-bearing silicate glasses, with the former dominant in glasses produced from Na2SO4-doped starting materials, and the latter more abundant in more reduced glasses. The 29Si MAS NMR and Raman spectra also revealed changes in the silicate network structure of the sulfur-bearing glasses, which can be interpreted in terms of changes in the chemical composition and sulfur speciation.  相似文献   

13.
The structure of 21 binary potassium, rubidium and cesium silicate glasses (in the range 15-50 mol% alkali oxide) was analyzed by 29Si single quantum and double quantum MAS NMR spectroscopy. Their glass transition temperatures (Tg) were measured by calorimetry. The chemical shifts and the relative abundance of Qn species correlate with the cationic field strength (Z/r) of the network modifier. A correlation is observed between Tg and the inverse of the entropy of mixing of the different Qn species, which is explained in the framework of the Adam-Gibbs relaxation theory. At high alkali content, up to 44% of the SiO4 tetrahedra are part of three-membered rings. At a given alkali content, the abundance of these rings increases with increasing cation size. The abundance of three-membered rings in K-silicate melts correlates with a temperature and a non-linear composition dependence of the heat capacity. It is also a possible cause for the anomalous volumetric behavior of potassium silicate glasses.  相似文献   

14.
Reduction of octahedral Fe in the crystalline structure of smectites influences, possibly controls, surface-sensitive physical and chemical properties. The purpose of this study was to investigate if reduction of structural Fe by Na-dithionite or bacteria affects the chemical environment of constituent cations in montmorillonite, employing solid state multinuclear (29Si and 27Al) magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Reduction of structural Fe resulted in a positive (down field) chemical shift of the main Si Q3 (Q3(0Al)) site which was strongly correlated with Fe(II) content and inferred that distortions in Si-OT (T=Si, Al) bond angles and Si-O bond lengths occur with increasing layer charge. The line width (W) of the 29Si Q3 signal also increased with increasing levels of reduction. No change occurred in the position of the peak maximum for the octahedral Al (27AlVI) signal; however, an increased W was observed for this peak with increasing Fe(II) content. These results are attributed to decreases in Si-O-T bond angles and Si-O bond distances, corresponding to a better fit between the tetrahedral and octahedral sheets brought about by the presence of Fe(II) in the clay structure. The increased 27AlVI signal width (W) may also be due to a lessening of the paramagnetic influence of Fe(III) nuclei and enhancement of 27AlVI signals with different quadrupole coupling constants (QCC). Multinuclear MAS NMR analyses of dithioniteand microbially-reduced montmorillonite indicate that reduction of structural Fe caused reversible changes in the smectite structure, at least as far as this method could discern.  相似文献   

15.
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.  相似文献   

16.
Compression of MgSiO3 glass in a 6/8 multianvil apparatus to 10.0 ± 0.5 GPa results in demonstrable changes in density and silicon coordination. Under high-pressure, samples were heated over a range of temperatures from 300 to 773 K, quenched to room temperature and decompressed at rates of 10.4 and 0.08 GPa/min. Recovered glasses have bulk densities that are 2.6-11.0% higher than the non-compressed glass. 29Si MAS NMR spectra of compressed glasses show narrowing of the [4]Si peak resulting from a reduction in the spread of the Si-O-Si bond angle distribution. After heating and rapid decompression, 29Si MAS NMR spectra of recovered glasses exhibit peaks assignable to [4]Si, [5]Si, and [6]Si with relative fractions of 0.945, 0.045, and 0.008, respectively. These changes in Si coordination and in Si-O-Si bond angle distribution with pressure only represent part of the structural changes associated with permanent densification of heated and unheated samples. The abundance of [6]Si is found to be insensitive to decompression rate, while [5]Si reverts to [4]Si on slow decompression at room temperature. These observations demonstrate that high-coordinated silicon species in MgSiO3 glass are formed on compression below glass transition temperatures and that pressure-induced structural changes can be preserved with rapid decompression. The ease with which [5]Si reverts to [4]Si during decompression suggests that the conversion of [4]Si → [5]Si principally involves short-range atomic displacement. The reversible and irreversible features of densification of MgSiO3 glass, provide insights into the fundamental structural and rheological properties of refractory silicate melts similar to those found in the Earth’s mantle.  相似文献   

17.
Estimation of the framework connectivity and the atomic structure of depolymerized silicate melts and glasses (NBO/T > 0) remains a difficult question in high-temperature geochemistry relevant to magmatic processes and glass science. Here, we explore the extent of disorder and the nature of polymerization in binary Ca-silicate and ternary Ca-aluminosilicate glasses with varying NBO/T (from 0 to 2.67) using O-17 NMR at two different magnetic fields of 9.4 and 14.1 T in conjunction with quantum chemical calculations. Non-random distributions among framework cations (Si and Al) are demonstrated in the variation of relative populations of oxygen sites with NBO/T. The proportion of non-bridging oxygen (NBO, Ca-O-Si) in the binary and ternary aluminosilicate glasses increases with NBO/T. While the trend is consistent with predictions from composition, the detailed fractions apparently deviate from the predicted values, suggesting further complications in the nature of polymerization. The proportion of each bridging oxygen in the glasses also varies with NBO/T. The fractions of Al-O-Si and Al-O-Al increase with increasing polymerization as CaO is replaced with Al2O3, while that of Si-O-Si seems to decrease, implying that activity of silica may decrease from calcium silicate to polymerized aluminosilicates (XSiO2=constant). Quantum chemical molecular orbital calculations based on density functional theory show that a silicate chain with Al-NBO (Ca-O-Al) has an energy penalty (calculated cluster energy difference) of about 108 kJ/mol compared with the cluster with Ca-O-Si, consistent with preferential depolymerization of Si-networks, reported in an earlier O-17 NMR study [Allwardt, J., Lee, S.K., Stebbins, J.F., 2003. Bonding preferences of non-bridging oxygens in calcium aluminosilicate glass: Evidence from O-17 MAS and 3QMAS NMR on calcium aluminate glass. Am. Mineral.88, 949-954]. These prominent types of non-randomness in the distributions suggest significant chemical order in silicate glasses that leads to a decrease in silica activity coefficient and will be useful in modeling transport properties of melts.  相似文献   

18.
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 KHSi2O5, 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 δiso for 29Si compared to that for anhydrous albite glass. The calculated δiso of 27Al in such linkages agrees with the experimental data, but shows an increase in Cq 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.  相似文献   

19.
Hydrous silica glasses containing 2.5 wt.% and 8.7 wt.% H2O were prepared by quenching melts from high pressures and temperatures, and investigated by 29Si NMR. Cross-polarisation magic angle spinning NMR experiments are described and used to identify silicon in different structural units within the glasses. The relative amounts of each structural unit are obtained by quantitative single pulse MASNMR and used together with the known water content to give the extent of hydroxyl formation. The hydroxyl concentration appears to be lower than that suggested by most previous work on hydrous silicate glasses using other experimental techniques.  相似文献   

20.
We present NMR spectroscopic data, obtained by 1H MAS, 1H static spin-echo, and 29Si{1H} CP-MAS techniques, for a series of hydrous magnesium silicate samples synthesized at high pressure. This series includes chondrodite, β-Mg2SiO4, and phases A, B, superhydrous B, and E. Phases B and superhydrous B give very narrow 29Si NMR peaks and display the most de-shielded SiVI chemical shifts yet reported: ?170.4?ppm for B and ?166.6 for superhydrous B. The 1H NMR spectra of B and superhydrous B confirm the presence of paired hydroxyls, as determined from refinement of the H positions from X-ray diffraction data. The 1H MAS NMR spectra of phase B contain peaks for the two distinct hydrogen positions, with chemical shifts of +4.7 and +3.3?ppm. The static 1H spectrum contains a powder pattern characteristic of a strongly coupled hydrogen pair, from which a dipolar coupling constant of 18.6(4)?kHz and inter-hydrogen distance of d(H–H)=1.86(2)?Å were obtained. Superhydrous B appears to give two poorly resolved 1H MAS peaks, consistent with the presence of two distinct hydrogen pairs in the P21 mn crystal structure. Analysis of its spin-echo spectrum gives d(H–H)=1.83(3)?Å, slightly shorter than for phase B. β-Mg2SiO4, coexisting with phases B and superhydrous B, appears to give 29Si{1H} CP-MAS signal, indicating that it contains significant H concentration. The 29Si chemical shifts for phases B, superhydrous B, and chondrodite, together with those reported previously for other Mg-silicates, show a good correlation with structural parameters.  相似文献   

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