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

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

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

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

Composition dependence of elasticity in aluminosilicate glasses

The elastic properties of two types of aluminosilicate (basaltic and rhyolitic) glasses have been studied using both Brillouin and Raman spectroscopy at ambient conditions. It has been found that the elastic moduli of the basaltic glasses decrease with increasing SiO₂ concentration. The shear moduli displayed the least dependence on SiO₂ content. The bulk moduli of the basaltic glasses strongly depend on the sum of the Q ³ and Q ⁴ anionic units. Among the modifiers, iron cations showed the strongest effect on the elastic properties of the rhyolitic glasses. For the elastic moduli of rhyolitic glasses, the major effect of alkaline earth cations is on shear modulus; however, both iron and alkali cations showed stronger effects on bulk modulus and similar relative contribution between bulk and shear moduli (based on the equivalent M⁺ cation). The dependences of elastic moduli on bulk NBO/T observed in both types of glasses suggest that the elastic modulus of an aluminosilicate glass depends on the concentration of effective modifying cations rather than the apparent concentration of all non-network-forming cations. An analysis of data also indicated that the ideal molar mixing model is failed in prediction of the elastic properties of the present multicomponent glasses by using the known parameters.     

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.     

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

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

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.     

Vitreous state in nature—Origin and properties

Vitreous materials are quite routinely found in natural settings. Most of them are aluminosilicates, which often occur in large deposits. Considering the geological formations in which naturally occurring vitreous aluminosilicates are found, they have generally remained stable for more than 1 Ma on the earth's surface, even in different geological and climatic environments. These non-crystalline solids played a very important role in the development of ancient human civilizations, long before the introduction of metallic tools. Today, however, the properties of natural glasses are of interest to mankind for completely different reasons. For example, industrial glasses are used today for encapsulating toxic wastes, especially radioactive waste, which remains active for centuries or more, in order to prevent the unwanted transfer of harmful materials to the environment. The chemical compositions of industrially produced glasses are in large part different from the compositions of natural glasses. Little is quantitatively known about the stability of industrial glasses over very long periods of time (>10,000 years). However, the physical and chemical stability of natural aluminosilicate glasses is known to extend over very long periods of time.The advancement of technological design to prevent or at least minimize the melt down of toxic waste during the encapsulation process is currently a major challenge, using glasses of natural chemical composition. Brecciated glass, which is found frequently in natural settings, provides a special clue to the possibility of producing vitreous solids by sintering glass fragments without melting the cullets. It is essential to prevent melting of the cullets because the melt has the potential of chemically reacting with the toxic waste.This paper summarizes the geological, chemical, and physical facts concerning naturally produced glasses, and seeks to establish a recognized database for further research in the domain of understanding the glass-forming processes that occur in nature. Furthermore, the authors hope to stimulate research into the utilization of natural resources that to solve the problem of storing of toxic waste safely.Major and trace element data have been collected over the past 100 years. These data constitute a sufficient basis for the chemical characterization of natural glasses. More information about the major elements is not required, in order to understand the chemical properties of these materials. On the other hand, large gaps in compositional data exist where other related components are concerned: e.g., in the case of “water-species”, with its different forms of bonding in silicates or oxygen (oxygen fugacity), CO₂-, sulphur - or hydrocarbons (methane)-, hydrogen-, chlorine-and fluorine-species. All these components have a significant impact on the properties of glasses, even when present only in minor quantities. Glass textures and crystal morphologies reflect the processes of nucleation and crystal growth in a glass-forming matrix during the cooling and reheating cycles which are currently not thoroughly understood. In nature, the processes that led to the formation of vitreous materials are very different from those used in the production of industrial glasses. The different genetic conditions under which glass formation occurs permit differentiation between magmatic and metamorphic vitreous solids. Sedimentary and biogenetic processes also contribute to the formation of non-crystalline solids.     

The geochemistry and provenance of Apollo 16 mafic glasses

The regolith of the Apollo 16 lunar landing site is composed mainly of feldspathic lithologies but mafic lithologies are also present. A large proportion of the mafic material occurs as glass. We determined the major element composition of 280 mafic glasses (>10 wt% FeO) from six different Apollo 16 soil samples. A small proportion (5%) of the glasses are of volcanic origin with picritic compositions. Most, however, are of impact origin. Approximately half of the mafic impact glasses are of basaltic composition and half are of noritic composition with high concentrations of incompatible elements. A small fraction have compositions consistent with impact mixtures of mare material and material of the feldspathic highlands. On the basis of major-element chemistry, we identified six mafic glass groups: VLT picritic glass, low-Ti basaltic glass, high-Ti basaltic glass, high-Al basaltic glass, KREEPy glass, and basaltic-andesite glass. These glass groups encompass 60% of the total mafic glasses studied. Trace-element analyses by secondary ion mass spectroscopy for representative examples of each glass group (31 total analyses) support the major-element classifications and groupings. The lack of basaltic glass in Apollo 16 ancient regolith breccias, which provide snapshots of the Apollo 16 soil just after the infall of Imbrium ejecta, leads us to infer that most (if not all) of the basaltic glass was emplaced as ejecta from small- or moderate-sized impacts into the maria surrounding the Apollo 16 site after the Imbrium impact. The high-Ti basaltic glasses likely represent a new type of basalt from Mare Tranquillitatis, whereas the low-Ti and high-Al basaltic glasses possibly represent the composition of the basalts in Mare Nectaris. Both the low-Ti and high-Al basaltic glasses are enriched in light-REEs, which hints at the presence of a KREEP-bearing source region beneath Mare Nectaris. The basaltic andesite glasses have compositions that are siliceous, ferroan, alkali-rich, and moderately titaniferous; they are unlike any previously recognized lunar lithology or glass group. Their likely provenance is within the Procellarum KREEP Terrane, but they are not found within the Apollo 16 ancient regolith breccias and therefore were likely deposited at the Apollo 16 site post-Imbrium. The basaltic-andesite glasses are the most ferroan variety of KREEP yet discovered.     

Disorder and the extent of polymerization in calcium silicate and aluminosilicate glasses: O-17 NMR results and quantum chemical molecular orbital calculations

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 (X_SiO2=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.     

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.     

On the origin of impact glass in the Apollo 16 regolith

This study addresses the issue of what fraction of the impact glass in the regolith of a lunar landing site derives from local impacts (those within a few kilometers of the site) as opposed to distant impacts (10 or more kilometers away). Among 10,323 fragments from the 64-210-μm grain-size fraction of three Apollo 16 regolith samples, 14% are impact glasses, that is, fragments consisting wholly or largely of glass produced in a crater-forming impact. Another 16% are agglutinates formed by impacts of micrometeorites into regolith. We analyzed the glass in 1559 fragments for major- and minor-element concentrations by electron probe microanalysis and a subset of 112 of the fragments that are homogeneous impact glasses for trace elements by secondary ion mass spectrometry. Of the impact glasses, 75% are substantially different in composition from either the Apollo 16 regolith or any mixture of rocks of which the regolith is mainly composed. About 40% of the impact glasses are richer in Fe, Mg, and Ti, as well as K, P, and Sm, than are common rocks of the feldspathic highlands. These glasses must originate from craters in maria or the Procellarum KREEP Terrane. Of the feldspathic impact glasses, some are substantially more magnesian (greater MgO/FeO) or have substantially lower concentrations of incompatible elements than the regolith of the Apollo 16 site. Many of these, however, are in the range of feldspathic lunar meteorites, most of which derive from points in the feldspathic highlands distant from the Procellarum KREEP Terrane. These observations indicate that a significant proportion of the impact glass in the Apollo 16 regolith is from craters occurring 100 km or more from the landing site. In contrast, the composition of glass in agglutinates, on average, is similar to the composition of the Apollo 16 regolith, consistent with local origin.     

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.     

Rb,Sr and strontium isotopic composition,K/Ar age and large ion lithophile trace element abundances in rocks and glasses from the Wanapitei Lake impact structure

Shock metamorphosed rocks and shock-produced melt glasses from the Wanapitei Lake impact structure have been examined petrographically and by electron microprobe. Eleven clasts exhibiting varying degrees of shock metamorphism and eight impact-produced glasses have been analyzed for Rb, Sr and Sr isotopic composition. Five clasts and one glass have also been analyzed for large ion lithophile (LIL) trace element abundances including Li, Rb, Sr, and Ba and the REE's.The impact event forming the Wanapitei Lake structure occurred 37 m.y. ago based on K/Ar dating of glass and glassy whole-rock samples. Rb/Sr isotopic dating failed to provide a meaningful whole-rock or internal isochron. The isotopic composition of the glasses can be explained by impact-produced mixing and melting of metasediments. Large ion lithophile trace element abundance patterns confirm the origin of the glasses by total shock melting of metasediments.     

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.     

Gas-hydrodynamic analysis of the genesis of green and orange glasses in lunar rocks

In order to elucidate the genesis of green and orange glasses in Apollo 15 and Apollo 17 samples of lunar rocks, two alternative hypotheses are analyzed, according to which the glasses are produced either (1) by a comet or meteorite impact (impact model) or (2) by volcanic activity (volcanic model). The green and orange glasses are clearly genetically and petrochemically autonomous, i.e., the composition of the glasses themselves differs from those of the major types of the primary rocks. The mechanisms responsible for the origin of the glasses are analyzed along with mathematical models of their genesis. The theoretically calculated size distribution of glass particles is in good agreement with those measured in Apollo 15 and Apollo 17 samples. Simulation results and the analysis of the composition and structure of the green and orange glasses lead to the conclusion that the impact hypothesis of their genesis is the most realistic.     

In-situ high-temperature Raman spectroscopic studies of aluminosilicate liquids

We have measured in-situ Raman spectra of aluminosilicate glasses and liquids with albite (NaAlSi₃ O₈) and anorthite (CaAl₂Si₂O₈) compositions at high temperatures, through their glass transition range up to 1700 and 2000 K, respectively. For these experiments, we have used a wire-loop heating device coupled with micro-Raman spectroscopy, in order to achieve effective spatial filtering of the extraneous thermal radiation. A major concern in this work is the development of methodology for reliably extracting the first and second order contributions to the Raman scattering spectra of aluminosilicate glasses and liquids from the high temperature experimental data, and analyzing these in terms of vibrational (anharmonic) and configurational changes. The changes in the first order Raman spectra with temperature are subtle. The principal low frequency band remains nearly constant with increasing temperature, indicating little change in the T-O-T angle, and that the angle bending vibration is quite harmonic. This is in contrast to vitreous SiO₂, studied previously. Above Tg, intensity changes in the 560–590 cm^?1 regions of both sets of spectra indicate configurational changes in the supercooled liquids, associated with formation of additional Al-O-Al linkages, or 3-membered (Al, Si)-containing rings. Additional intensity at 800 cm^?1 reflects also some rearrangement of the Si-O-Al network.     

Effects of the degree of polymerization on the structure of sodium silicate and aluminosilicate glasses and melts: An O NMR study

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 δ_iso) 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.     

Shock produced rock glasses from the Ries crater

In the suevite breccia of the Ries impact crater, Germany, glasses occur as bombs, and small particles in the groundmass. These glasses were formed from melt produced by shock fusion of crystalline basement rocks. Ejection from the crater resulted in the formation of aerodynamically shaped bombs, a few homogeneous spherules and a large mass of small glass particles which were deposited in the suevite breccia. Bombs and small particles included within chilled bottom and top layers of suevite deposits have been preserved in vitreous state, whereas glasses within the interior of the suevite devitrified, due to slower cooling rates.This paper summarizes the results of petrographical and chemical investigations of suevite glasses and their devitrification products. Conclusions are derived on origin and history of bombs and glass particles.Vitreous bombs and glass particles consist of schlieren-rich glass, mineral fragments (mainly quartz), rock fragments and vesicles. Wet chemical, trace element and microprobe analyses reveal that a primary melt was formed by shock fusion of a basement complex, consisting of about 80% biotite granite and 20% amphibolite. The, originally, more than 1800° C hot melt then incorporated shocked and desintegrated rocks of outer zones of the impact. Partial fusion of the rock debris resulted in a polyphase mixture consisting of melts, different in composition, accumulations of refractory mineral fragments and vesicles.Devitrified bombs and glass particles which are found in the interior of suevite deposits show alterations of texture and composition, due to microcrystallite growth and action of hydrothermal and weathering solutions. Incipient devitrification is indicated by brown staining of the glasses, originating, probably, by exsolution of minute magnetite particles. By optical microscopy and X-ray analysis, plagioclase and pyroxenes have been identified as main devitrification products. Shapes and textures of microcrystallites indicate fast crystal growth in a viscous and supercooled medium. Hot fluids permeating the suevite deposited microcrystalline quartz in vesicles and cracks. Later, montmorillonite was precipitated by solutions corroding the glass. Action of solutions on glasses which were weakened in coherence by devitrification resulted in oxidation of iron, leaching of iron and magnesium, and enrichment in alkalis.     

Condensate glasses from the Zhamanshin crater. I. Irghizites

The presence of condensate glass was established for the first time in natural terrestrial impact glasses. Its existence was previously predicted on the basis of shock evaporation experiments. Condensate glass was found in the irghizites of the Zhamanshin crater. Its characteristic features were described, including a combination of high silica content with the presence of nanoscale crystalline nuclei and typical globular morphology under TEM.