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1.
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   

2.
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   

3.
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 δiso, quadrupolar coupling constant CQ and quadrupolar asymmetry parameter ηQ) 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.  相似文献   

4.
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   

5.
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   

6.
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   

7.
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   

8.
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   

9.
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   

10.
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   

11.
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 (AlIV), but a small amount of five-coordinate Al (AlV) is also observed in all the anhydrous and hydrous glasses. Furthermore, six-coordinate Al (AlVI) is also present in most of the hydrous glasses. As Al of higher coordinations are favored by high pressure, AlVIOH and AlVOH may become major water species at higher pressures corresponding to those of the Earth’s mantle.  相似文献   

12.
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   

13.
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   

14.
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 (H2Omol). 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 H2Omol, can be predicted for the entire range of water and Al contents.  相似文献   

15.
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   

16.
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly.  相似文献   

17.
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   

18.
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   

19.
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   

20.
As part of a study of the effect of geologically common network modifiers on polymerization in silicate melts, glasses, and silica-rich aqueous solutions, we have studied the energies, electronic structures, and inferred chemical properties of IVT-O-IVT linkages in the tetrahedral dimers H6,Si2O7, H6AlSiO71?, and H6Al2O72? using semi-empirical molecular orbital theory (CNDO/2). Our results indicate that the electron donating character of the bridging oxygen, O(br), linking two tetrahedra increases with increasing T-O(br) bond length but decreases with decreasing T-O(br)-T angles and increasing O-T-O(br) angles. This increase or decrease of the donor character of O(br) coincides with an increase or decrease of the affinity of O(br) for hard acceptors. The calculated electronic structure for the H6Si2O7 molecule is compared with the observed X-ray emission, absorption, and photoelectron spectra of quartz and vitreous silica; the reasonable match between calculated and observed oxygen Kα emission spectra of vitreous silica supports our assertion that non-bonded O(br) electron density energetically at the top of the valence band controls the chemical reactivity of IVT-O-IVT linkages in polymerized tetrahedral environments.  相似文献   

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