An X-ray diffraction study of shock-wave-densified SiO<Subscript>2</Subscript> glasses

 The densification and structural changes in SiO₂ glass compressed up to 43.4 GPa by shock experiments are investigated quantitatively by the X-ray diffraction technique. Direct structural data (average Si–O and Si–Si distances and Si–O–Si angles, coordination number of the Si atom) of these shock-densified SiO₂ glasses have been obtained by analyzing the radial distribution function curves, RDF(r), calculated with X-ray diffraction data. The coordination number of all densified glasses is about 4 and shows almost no pressure variation. The SiO₂ glass has shown density increase of 11% at a shock compression of 26.3 GPa. This density evolution could not be explained by the coordination change. The reduction of the average Si–O–Si angle (144° at 0 GPa to 136° at 26.3 GPa) obtained from RDF(r) data may account for this density increase. This Si–O–Si angle change may be caused by shrinkage of the network structure and the increase of small rings of SiO₄ tetrahedra. For higher shock pressure, a decrease in the Si–O–Si angle to 140° was observed. This is consistent with the decrease in density at 32.0 and 43.2 GPa. This decrease in the Si–O–Si angle and density could be attributed to an annealing effect due to high after-shock residual temperature. This pressure dependence of average Si–O–Si angles in shock-densified SiO₂ glass agrees with the results of our previous Raman spectroscopic study. On the other hand, the pressure variation for the first sharp diffraction peak (FSDP) was analyzed to estimate the evolution of intermediate range structures. It is suggested that the mean d value (d _m ) obtained from the position of FSDP strongly depends on the shock and residual temperature, as well as shock pressure. Received: 29 June 2001 / Accepted: 14 November 2001     

A Raman spectroscopic study of shock-wave densification of anorthite (CaAl2Si2O8) glass

Structural modifications induced by shock-wave compression up to 40 GPa in anorthite glass are investigated by Raman spectroscopy. In the first investigation, densification increases with increasing shock pressure. A maximum densification of 2.2% is obtained for a shock pressure of 24 GPa. This densification is attributed to a decrease of the average ring size, favoring three-membered rings. The densification is much lower than in silica glass subject to shock at similar pressures (11%), because the T-O-T bond angle decrease is impeded in anorthite glass. For higher shock pressures, the decrease of the recovered densification is attributed to partial annealing of the samples due to high after-shock residual temperatures. The study of the annealing process of the most densified glass by in-situ high temperature Raman spectroscopy confirms that relaxation of the three-membered rings occurs above about 900 K. Received: 21 July 1998 / Revised and accepted: 27 January 1999     

Structural evolutions of an obsidian and its fused glass by shock-wave compression

Shock-recovery experiments for obsidian and its fused glass have been carried out with pressure up to 35 GPa. Structural evolution accompanying the shock compression was investigated using X-ray diffraction technique, Raman and infrared spectroscopy. The densities of obsidian and its fused glass increased with applied shock pressure up to 25 GPa. Densification reached a maximum of 4.7 and 3.6% for obsidian and its fused glass, respectively. The densification mechanism is attributed to reduction of the T–O–T angle, and changes in ring statistics in the structure. Density reduction observed at greater than 25 GPa of applied shock pressure is due to partial annealing of the high-density glass structures brought by high post-shock residual temperature. The density of fused glass is almost equal to its original value at 35 GPa while the shocked obsidian has a slightly lower value than its original value. Amorphization of crystallites present in the obsidian due to shock compression is probably the cause of the density decrease. The structural evolution observed in shock-compressed obsidian and its fused glass can be explained by densification resulting from average T–O–T angle reduction and increase of small rings, and subsequent structural relaxation by high post-shock temperature at applied shock compression above 25 GPa.     

Raman spectroscopic study of hydrous <Emphasis Type="Italic">γ</Emphasis>-Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> to 56.5 GPa

 Raman spectra of a single-crystal fragment of hydrous γ-Mg₂SiO₄, synthesized in a multianvil press, have been measured in a diamond-anvil cell with helium as pressure-transmitting medium to 56.5 GPa at room temperature. All five characteristic spinel Raman modes shift continuously up to the highest pressure, showing no evidence for a major change in the crystal structure despite compression well beyond the stability field of ringwoodite in terms of pressure. At pressures above ∼30 GPa a new mode on the low-frequency site of the two silicate-stretching modes is clearly identifiable, indicating a modification in the spinel structure which is reversible on pressure release. The frequency of the new mode (802 cm⁻¹ extrapolated to 1 bar) suggests the presence of Si–O–Si linkages and/or a partial increase in the coordination of Si. Direct determination of the subtle structural change causing the new Raman mode would require high-pressure, single-crystal synchrotron X-ray diffraction experiments. The Raman modes of hydrous and anhydrous Mg-end-member ringwoodite are nearly identical up to 20 GPa, suggesting that protonation has only minor effect on the lattice dynamics over the entire pressure stability range for ringwoodite in the mantle. Received: 7 December 2001 / Accepted: 16 April 2002     

A hitherto unrecognised band in the Raman spectra of silica rocks: influence of hydroxylated Si–O bonds (silanole) on the Raman moganite band in chalcedony and flint (SiO<Subscript>2</Subscript>)

Chalcedony is a spatial arrangement of hydroxylated nanometre-sized α-quartz (SiO₂) crystallites that are often found in association with the silica mineral moganite (SiO₂). A supplementary Raman band at 501 cm⁻¹ in the chalcedony spectrum, attributed to moganite, has been used for the evaluation of the quartz/moganite ratio in silica rocks. Its frequency lies at 503 cm⁻¹ in sedimentary chalcedony, representing a 2 cm⁻¹ difference with its position in pure moganite. We present a study of the 503 cm⁻¹ band’s behaviour upon heat treatment, showing its gradual disappearance upon heating to temperatures above 300 °C. Infrared spectroscopic measurements of the silanole (SiOH) content in the samples as a function of annealing temperature show a good correlation between the disappearance of the 503 cm⁻¹ Raman band and the decrease of structural hydroxyl. Thermogravimetric analyses reveal a significant weight loss that can be correlated with the decreasing of this Raman band. X-ray powder diffraction data suggest the moganite content in the samples to remain stable. We propose therefore the existence of a hitherto unknown Raman band at 503 cm⁻¹ in chalcedony, assigned to ‘free’ Si–O vibrations of non-bridging Si–OH that oscillate with a higher natural frequency than bridging Si–O–Si (at 464 cm⁻¹). A similar phenomenon was recently observed in the infrared spectra of chalcedony. The position of this Si–OH-related band is nearly the same as the Raman moganite band and the two bands may interfere. The actually observed Raman band in silica rocks might therefore be a convolution of a silanole and a moganite vibration. These findings have broad implications for future Raman spectroscopic studies of moganite, for the assessment of the quartz/moganite ratio, using this band, must take into account the contribution from silanole that are present in chalcedony and moganite.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

High-pressure Raman spectroscopic study of Fo90 hydrous wadsleyite

Raman spectra of monoclinic Fo₉₀ hydrous wadsleyite with 2.4 wt% H₂O have been measured in a diamond-anvil cell with helium as a pressure-transmitting medium to 58.4 GPa at room temperature. The most intense, characteristic wadsleyite modes, the Si–O–Si symmetric stretch at 721 cm⁻¹ and the symmetric stretch of the SiO₃ unit at 918 cm⁻¹, shift continuously to 58.4 GPa showing no evidence of a first order change in the crystal structure despite compression well beyond the stability field of wadsleyite in terms of pressure. The pressure dependence of these two modes is nearly identical for Fo₉₀ hydrous and Fo₁₀₀ anhydrous wadsleyite. A striking feature in the high-pressure Raman spectra of Fo₉₀ hydrous wadsleyite is the appearance of new Raman modes above 9 GPa in the mid-frequency range (300–650 cm⁻¹ at 1-bar and shifted to 500–850 cm⁻¹ at 58.4 GPa) accompanied by a significant growth in their intensities under further compression. In the OH stretching frequency range Fo₉₀ hydrous wadsleyite exhibits a larger number of modes than the Mg end-member phase. The higher number of modes may be due to either additional protonation sites or simply that we observe a different subset of all possible OH modes for each sample. The high-pressure behaviour of the OH stretching modes of Fo₉₀ and Fo₁₀₀ hydrous wadsleyite is consistent: OH stretching modes with frequencies <3,530 cm⁻¹ decrease with increasing pressure whereas the higher-frequency OH modes show a close to constant pressure dependence to at least 13.2 GPa. The approximately constant pressure dependence of the OH modes above 3,530 cm⁻¹ is consistent with protons being located at the O1···O edges around M3.     

Compression mechanisms of coesite

 The structure of coesite has been determined at ten pressures up to a maximum of 8.68 GPa by single-crystal X-ray diffraction. The dominant mechanism of compression is the reduction of four of the five independent Si–O–Si angles within the structure. There is no evidence of the fifth linkage, Si1–O1–Si1, deviating from 180°. Some Si–O bond distances also decrease by up to 1.6% over the pressure range studied. The pattern of Si–O–Si angle reduction amounts to a rotation of the Si2 tetrahedron around the [001] direction. This rotation induces significant internal deformation of the Si1 tetrahedron. Comparison of the experimental data with rigid-unit distance least-squares simulations of coesite suggests that this pattern of compression, the anomalous positive values of both s₂₃ and K′′ in the equation of state of coesite, its high elastic anisotropy and the unusual straight Si1–O1–Si1 linkage within the structure are all consequences of the connectivity of the tetrahedral framework. Received: 11 July 2002 / Accepted: 14 January 2003 Acknowledgements The help of Christian Baerlocher of ETH Zurich in providing both the DLS-76 software and advice in its use is gratefully acknowledged, as are discussions with Paul Ribbe of Virginia Tech and the comments of two anonymous reviewers. The data analysis was supported by the National Science Foundation under grant EAR-0105864 to N.L. Ross and R.J. Angel.     

Visualization-based analysis of structural and dynamical properties of simulated hydrous silicate melt

We have explored first-principles molecular dynamics simulation data for hydrous MgSiO₃ liquid (with 10 wt% water) to gain insight into its structural and dynamical behavior as a function of pressure (0–150 GPa) and temperature (2,000–6,000 K). By visualizing/analyzing a number of parameters associated with short- and mid-range orders, we have shown that the melt structure changes substantially on compression. The speciation of the water component at low pressures is dominated by the isolated structures (with over 90% hydrogen participated) consisting of hydroxyls, water molecules, O–H–O bridging and four-atom (O–H–O–H and H–O–H–O) groups, where every oxygen atom may be a part of polyhedron or free (i.e., bound to only magnesium atom). Hydroxyls favor polyhedral sites over magnesium sites whereas molecular water is almost entirely bound to magnesium sites, and also interpolyhedral bridging (Si–O–H–O–Si) dominates other types of bridging. Water content is shown to enhance and suppress, respectively, the proportions of hydroxyls and molecular water. As compression increases, these isolated structures increasingly combine with each other to form extended structures involving a total of five or more O and H atoms and also containing threefold coordination species, which together consume over 80% hydrogen at the highest compression studied. Our results show that water lowers the mean coordination numbers of different types including all cation–anion environments. The hydrous melt tends to be more tetrahedrally coordinated but with the Si–Si network being more disrupted compared to the anhydrous melt. Protons increase the content of non-bridging oxygen and decrease the contents of bridging oxygen as well as oxygen triclusters (present at pressures above 10 GPa). The calculated self-diffusion coefficients of all atomic species are enhanced in the presence of water compared to those of the anhydrous melt. This is consistent with the prediction that water depolymerizes the melt structure at all pressures. Our analysis also suggests that proton diffusion involves two processes—the transfer of H atoms (requiring the rupture and formation of O–H bonds) and the motion of hydroxyls as hydrogen carriers (requiring the rupture and formation of Si–O and/or Mg–O bonds). Both the processes are operative at low compression whereas only the first process is operative at high compression.     

High-pressure and high-temperature Raman spectroscopic study of hydrous wadsleyite (β-Mg2SiO4)

In situ Raman spectra of hydrous wadsleyite (β-Mg₂SiO₄) with ~1.5 wt% H₂O, synthesized at 18 GPa and 1,400°C, have been measured in an externally heated diamond anvil cell up to 15.5 GPa and 673 K. With increasing pressure (at room temperature), the three most intense bands at ~549, 720 and 917 cm⁻¹ shift continuously to higher frequencies, while with increasing temperature at 14.5 GPa, these bands generally shift to lower frequencies. The temperature-induced frequency shifts at 14.5 GPa are significantly different from those at ambient pressure. Moreover, two new bands at ~714 and ~550 cm⁻¹ become progressively significant above 333 and 553 K, respectively, and disappear upon cooling to room temperature. No corresponding Raman modes of these two new bands were reported for wadsleyite at ambient conditions, and they are thus probably related to thermally activated processes (vibration modes) at high-pressure and temperature conditions.     

High-pressure Raman spectroscopic study of chondrodite

Variation of Raman spectra of both natural (F-bearing) and synthetic (F-free) chondrodite samples were studied up to 400 kbar at room temperature. Ambient Raman frequencies for the synthetic sample are in general lower than those for the natural one. This is correlated with a slight expansion of the volume of the synthetic sample due to substitution of OH for F. The frequencies of all Raman bands for both samples increase monotonically with increasing pressure. The positive pressure dependences in the O−H stretch frequencies for both F-free and F-bearing samples are contrary to those for other dense hydrous magnesium silicates. A mechanism involving both the hydrogen-hydrogen repulsion and hydrogen bondings is proposed to explain the abnormal behavior. The effects of substitution of F for OH on both the ambient and high-pressure Raman spectra of chondrodite are also discussed. Received: 19 February 1998 / Revised accepted: 26 June 1998     

Reaction of forsterite with hydrogen molecules at high pressure and temperature

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H₂ molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.     

High-temperature X-ray diffraction and Raman spectroscopy of diopside and pseudowollastonite

Diopside (CaMgSi₂O₆) and pseudowollastonite (CaSiO₃) have been studied by X-ray powder diffraction and Raman spectroscopy up to their respective melting points. In agreement with previous unit-cell parameters determinations below 1100 K, thermal expansion of diopside along the a and c axis is much smaller than along the b axis. For pseudowollastonite, the axis expansivity increases slightly in the order b>a>c. For both minerals, the change in unit-cell angles is very small and there are no anomalous variations of the other unit-cell parameters near the melting point. With increasing temperatures, the main changes observed in the Raman spectra are strong increases of the linewidths for those bands which mainly represent Si−O−Si bending (near 600 cm⁻¹) or involve Ca−O or Mg−O stretching, in the range 270–500 cm⁻¹ for diopside, and 240–450 cm⁻¹ for pseudowollastonite. At temperatures near the onset of calorimetric premelting effects, this extensive band widening results in a broad Raman feature that can no longer be deconvoluted into its individual components. No significant changes affect the Si−O streching modes. For both diopside and pseudowollastonite, premelting appears to be associated with enhanced dynamics of the alkaline-earth elements. This conclusion contrasts markedly with that drawn for sodium metasilicate in which weaker bonding of sodium allows the silicate framework to distort and deform in such a way as to prefigure the silicate entities present in the melt. Received 16 July 1997 / Revised, accepted: 6 March 1998     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

The structure of sodium tetrasilicate glass from neutron diffraction, reverse Monte Carlo simulations and Raman spectroscopy

The reverse Monte Carlo (RMC) method was used for modelling the three-dimensional structure of sodium tetrasilicate glass (Na₂Si₄O₉, NS4). Neutron diffraction data over a large momentum transfer range and nuclear magnetic resonance results (Q-species distribution) as well as chemical bonding considerations have been used to constrain the RMC simulations. Very good agreement with the experimental structure factor was achieved. The three-dimensional model is analysed in terms of partial pair distribution functions, bond-angle distributions, short-range order (SRO) clusters and ring statistics. The average Si–O–Si bridging angle is different for the different Qⁱ–Q^j units. The effect of different Q species on the network connectivity is analysed by comparison with statistical SRO distributions. While the Q² species are randomly distributed, a high preference for the formation of Q⁴–Q⁴ units in three-membered rings is found. This explains why during the initial stages of hydration of NS4 glass, Si–OH groups are preferentially formed by breaking Q⁴–Q⁴ linkages. The RMC model also provides an independent test for the assignment of bands in the Si–O stretching region of the Raman spectrum. It is shown that the bands at about 1050 and 1100 cm⁻¹ are probably due to Q³ units surrounded by different numbers of Q⁴ units. Received: 7 April 1997 / Revised, accepted: 5 July 1997     

The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite

Density functional theory calculations have been used to study the pressure-induced changes of the hydrogen bond of Fe-free orthozoisite and clinozoisite and the concomitant shifts of the OH-stretching frequencies. Two independent parameter-free lattice dynamical calculations have been employed. One was based on a plane-wave basis set in conjunction with norm-conserving pseudopotentials and a density functional perturbation theory approach, while the other used a localised basis set and a finite displacement algorithm for the lattice dynamical calculations. Both models confirm the unusually large pressure-induced red-shift found experimentally (−33.89 cm⁻¹/GPa) in orthozoisite, while the pressure-induced shifts in clinozoisite are much smaller (−5 to −9 cm⁻¹/GPa). The atomistic model calculations show that in orthozoisite the nearly linear O–H⋯O arrangement is compressed by about 8% on a pressure increase to 10 GPa, while concomitantly the O–H distance is significantly elongated (by 2.5% at 10 GPa). In clinozoisite, the O–H⋯O arrangement is kinked at ambient conditions and remains kinked at high pressures, while the O-H distance is elongated by only 0.5% at 10 GPa. The current calculations confirm that correlations between the distances and dynamics of hydrogen bonds, which have been established at ambient conditions, cannot be used to infer hydrogen positions at high pressures.     

Hydrostatic compression and crystal structure of pyrope to 33 GPa

The equation of state and crystal structure of pyrope were determined by single crystal X-ray diffraction under hydrostatic conditions to 33 GPa, a pressure that corresponds to a depth of about 900 km in the lower mantle. The bulk modulus K _T0 and its pressure derivative K ^' _T0 were determined simultaneously from an unweighted fit of the volume data at different pressures to a third order Birch-Murnaghan equation of state. They are 171(2) GPa and 4.4(2), respectively. Over the whole pressure range, MgO₈ polyhedra showed the largest compression of 18.10(8)%, followed by AlO₆ and SiO₄ polyhedra, with compression of 11.7(1)% and 4.6(1)%, respectively. The polyhedral bulk moduli for MgO₈, AlO₆ and SiO₄ are 107(1), 211(11) and 580(24) GPa, respectively, with K ^' _T0 fixed to 4. Significant compression of up to 1.8(1)% in the very rigid Si−O bonding in pyrope could be detected to 33 GPa. Changes in the degree of polyhedral distortion for all three types of polyhedra could also be observed. These changes could be found for the first time for AlO₆ and SiO₄ in pyrope. It seems that the compression of pyrope crystal structure is governed by the kinking of the Al−O−Si angle between the octahedra and tetrahedra. No phase transition could be detected to 33 GPa. Received: 24 March 1997 / Revised, accepted: 29 July 1997     

LiFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> at low temperatures: an infrared spectroscopic study

 Synthetic aegirine LiFeSi₂O₆ and NaFeSi₂O₆ were characterized using infrared spectroscopy in the frequency range 50–2000 cm⁻¹, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi₂O₆, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi₂O₆ (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P2₁/c structural phase transition of LiFeSi₂O₆ is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm⁻¹ in the monoclinic P2₁/c phase, which is due to the Si–O–Si vibration in the Si₂O₆ chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm⁻¹ show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi₂O₆ measured at low temperatures, the change in LiFeSi₂O₆ is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P2₁/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002     

In situ Raman spectroscopy on kerogen at high temperatures and high pressures

Kerogen samples were treated at temperatures and pressures up to 25–600°C and ~9 GPa, respectively. In situ micro-Raman spectroscopy was used to measure the systematic changes in the first-order Raman spectral features during the process of temperature or pressure increment. Three Raman bands, D1, D2, and G bands, were examined to characterize the structural and chemical changes of kerogen at high temperatures and pressures. We found that the wavenumbers of D1, D2 and G bands showed a linear variation with both temperature and pressure. Therefore, a correlation between R1 and R2 and the peak temperature in regionally metamorphosed rocks cannot be applied to this work. This result implies that the G band may serve as a temperature or pressure indicator during the promotion of maturation of kerogen. Kerogen possesses reversible properties in contrast with the natural samples recovered from the field suffered from prolonged thermal history during regional metamorphism.     

Raman-spectroscopy and X-ray diffractometer studies of experimentally produced diaplectic feldspar glass

Raman vibrational spectra and X-ray diffractometer scans were obtained from experimentally shocked samples of oligoclase (An₁₉) and andesine (An₄₉). Some 11 oligoclase and 15 andesine targets were shocked between 24 and 40 GPa to address the transition from crystalline to diaplectic states and to explore differences in the structural state of diaplectic feldspar glasses (maskelynite) as a function of peak shock stress. Thy symmetrical VS (T-O-T) (T=Si or Al) stretch bands are the most persistent. They disappear, however, in the noise of an unusually strong luminescent spectrum at > 32 GPa in the oligoclase and at > 30 GPa in the andesine; i.e., at pressures where transition to diaplectic glass is complete. The Raman investigations yield a maskelynite structure that is probably one of a multitude of very small domains with some order, but with a large range of local properties on the scale of small domains, either in heterogeneous size-distribution of domains or in their detailed order, if not both. This results in a very large number of Raman photon-phonon frequencies unlike glasses derived from quenched melts. Our study corroborates conclusions by others, that diaplectic glasses may be the quench products of very dense, disordered phases that exist during shock compression and that subsequently relax to these unusually dense glasses that are only known from shock processes. An origin by relaxation of highly ordered, genuine high pressure polymorphs possessing the structure of hollandite is unlikely, as no evidence for any six-fold Si-coordination was found. Detailed luminescent emission spectra were taken of the oligoclase samples and they show disappearance of the IR band and a strengthening of the green band (the blue band could not be detected with a primary radiation of wavelength 448 nm). This supports previous views that the disappearance of IR emission is most likely caused by shock-induced changes of the crystal field near Fe³⁺ sites, rather than due to quenching by Fe²⁺. The X-ray studies were primarily intended to explore whether differences in structural states of maskelynite occur on sufficiently large scales to be detected by standard diffractometry methods. This is not the case. X-ray diffractometer patterns are grossly similar, if not identical, in samples shocked between 30 and 40 GPa and may not be used to fine-tune the shock histories of naturally produced diaplectic glasses.