Cathodoluminescence microanalysis of silica and amorphized quartz

Cathodoluminescence (CL) techniques are used to investigate the defect structures of pure synthetic silicon dioxide (SiO₂) polymorphs. Pure, synthetic Types I, II, III and IV amorphous SiO₂ polymorphs, pure, synthetic crystal α-SiO₂ and pure, synthetic amorphized crystal α-SiO₂ have been investigated and their characteristic defects have been determined and compared. The CL emission from pure SiO₂ polymorphs is generally related to local point defects in the tetrahedrally coordinated SiO₂ host lattice. A range of CL emissions associated with non bridging oxygen defects, oxygen deficient defects and the radiative recombination of self trapped excitons are observed from both the pure synthetic crystal and amorphous SiO₂ polymorphs. In addition CL emissions associated with residual concentrations of Aluminium impurities are also observed from α-SiO₂ (quartz) and Type I and II a-SiO₂ (fused quartz). Localised amorphous micro-volumes may exist within natural α-SiO₂ due to the presence of a high concentration of pre-existing or induced defects. Amorphization of α-SiO₂ diminishes the difference between the defect structures and associated CL from α-SiO₂ and a-SiO₂. Thus CL investigation of the defect structure of a-SiO₂ polymorphs provides useful insight into the microstructure of amorphized α-SiO₂.     

Some physical properties of amorphous SiO2 synthesized by shock compression of α quartz

The amorphous phase of SiO₂ produced upon recovery of shock-compressed quartz demonstrates a wide range of refractive indices which can be correlated to the shock state. Both infra-red absorption spectra and X-ray diffraction patterns indicate that the shock-produced amorphous SiO₂ has a statistically more-random atomic distribution and longer Si-O and shorter Si-Si separation than does fused silica. By accounting for phase transformation, the calculated values of the shock and residual temperature are much higher than those obtained by Wackerle (1962) to a pressure of 700 kbar. Our results are consistent with experimental ones.     

Production of amorphous hydrated impure magnesium carbonate through ex situ carbonation

The evaluation of the feasibility of ex situ carbonation in landfills utilizing raw natural substances (namely serpentinites as Mg-source and the CO₂-rich fraction of biogas as C-source) was tested through a laboratory procedure comprising three steps. The first step is the acid attack of a serpentinite at 70 °C, by means of HCl 2 M, to get MgCl₂-rich solutions. Attacks of different durations were performed to evaluate the time needed. The second step is the neutralization of the MgCl₂-rich solution by addition of concentrated ammonia. The third (carbonation) step is mixing of the neutralized MgCl₂-rich solution with a solution of ammonium carbonate. This was produced in a landfill by absorption of CO₂ contained in biogas in a solution of ammonia. The neutralization of acid MgCl₂-rich solutions caused the precipitation of ferrihydrite with secondary ammonium carnallite and salammoniac, whereas abundant precipitation of Amorphous Hydrated Impure Magnesium Carbonate (AHIMC), sometimes with minor nesquehonite, occurred in the third step. This solid carbonate acts as a stable CO₂ sink up to 380 °C. The geochemical behavior of some minor elements was also investigated during the experimental processes revealing that Al, Cr and Ni were removed during neutralization (second step), in contrast to Ca which remained in the circumneutral MgCl₂-rich solution and entered into the structure of AHIMC. During the carbonation step, precipitation of artinite, hydromagnesite, lansfordite, magnesite and nesquehonite was thermodynamically impossible as the aqueous phase was undersaturated with respect to these solid phases upon separation of AHIMC.     

Glass transitions and thermodynamic properties of amorphous SiO2, NaAlSinO2n+2 and KAlSi3O8

A drop calorimetric study, between 900 and 1800 K, of amorphous SiO₂, NaAlSi₃O₈, NaAlSi₂O₆, NaAlSiO₄ and KAlSi₃O₈ shows the increase in heat capacity which results from glass transitions. For these glasses, the fictive temperature has a negligible effect on the heat capacity above room temperature, but it has an important influence on the enthalpy of formation as obtained from solution calorimetry. From these results and published Cp and enthalpy of solution data, several properties have been calculated: the enthalpies of fusion of high albite, nepheline, Jadeite and high sanidine, the thermodynamic functions of amorphous NaAlSi₃O₈ and KAlSi₃O₈ between 0 and 2000 K, and some mixing properties of liquids along the join SiO₂-NaAlSi₃O₈. The latter data suggest that these liquids behave more closely as athermal solutions than as regular solutions.     

Cathodoluminescence of synthetic and natural calcite: the effects of manganese and iron on orange emission

Summary The orange cathodoluminescence (CL) of calcite is known to be due to the presence of Mn²⁺ cations. It has been demonstrated here using CL and electron paramagnetic resonance (EPR) crossed analysis from synthetic calcite that neither Fe²⁺ nor Fe³⁺ ions influence this luminescence emission. More complex natural calcium carbonates have been investigated to check whether or not this conclusion can be applied to them. For this purpose, different white marbles from Greek quarries were analysed with CL. The data are completed with neutron activation analysis (NAA) for manganese and iron contents. Again it is shown that only manganese plays a role in the orange CL of these white marbles. This result provides an important clue in the wide field of provenance determination of calcium carbonate used in ancient art.Received February 19, 2002; revised version accepted October 22, 2002 Published online March 10, 2003     

Significance of an amorphous SiO2 phase in a pseudomorph after coesite enclosed in garnet from ultrahigh‐pressure eclogite,Su–Lu Belt,eastern China

Here, we report the first discovery of an amorphous SiO₂ phase (APSI phase) in a pseudomorph after coesite included in garnet from an ultrahigh‐pressure (UHP) eclogite from the Su–Lu metamorphic belt, eastern China. Using transmission electron microscopy, Raman spectroscopy and selected area electron diffraction, we show that the internal structure of the pseudomorph consists of an APSI phase with nano/submicrocrystalline particles of quartz and a polycrystalline K‐bearing fibrous sheet‐silicate phase (KFSS phase). The APSI phase‐bearing aggregates included in the garnet might have formed by reactions involving a supercritical fluid during exhumation by the following processes: (1) the development of radial cracks within the host garnet by the phase transition of coesite to quartz; (2) the decomposition of a part of the pseudomorph following infiltration of supercritical fluid; (3) the precipitation of the KFSS phase from the fluid phase during subsequent exhumation and cooling, which was likely promoted by a change in the metamorphic fluid from supercritical and/or subcritical to aqueous fluid; and (4) the rapid precipitation of the APSI phase under a metastable (non‐equilibrium) state, such as quenching, during a later stage of the exhumation. Whether the APSI phase generally formed during exhumation and survived widely throughout the Su‐Lu terrane is unknown. However, the presence of the APSI phase in a UHP eclogite provides new insight into the geodynamic phenomena occurring at continental collision zones.     

Garnet and spinel lherzolite assemblages in MgO–Al2O3–SiO2 and CaO–MgO–Al2O3–SiO2: thermodynamic models and an experimental conflict

The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al₂O₃–SiO₂ (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO₂ (CMS) and MgO–Al₂O₃–SiO₂ (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.     

Experiments on silicate melt immiscibility in the system Fe2SiO4–KAlSi3O8–SiO2–CaO–MgO–TiO2–P2O5 and implications for natural magmas

The effect of CaO and MgO, with or without TiO₂ and P₂O₅, on the two-melt field in the simplified system Fe₂SiO₄–KAlSi₃O₈–SiO₂ has been experimentally determined at 1,050°–1,240°C, 400 MPa. Despite the suppressing effect of MgO, CaO, and pressure on silicate melt immiscibility, our experiments show that this process is still viable at mid-crustal pressures when small amounts (0.6–2.0 wt%) of P₂O₅ and TiO₂ are present. Our data stress that the major element partition coefficients between the two melts are highly correlated with the degree of polymerisation (nbo/t) of the SiO₂-rich melt, whatever temperature, pressure, or exact composition. Experimental immiscible melt compositions in natural systems at 0.1 MPa from the literature (lunar and tholeiitic basalts) plot on similar but distinct curves compared to the simplified system. These relations between melt polymerisation and partition coefficients, which hold for a large range of compositions and fO₂, are extended to various volcanic and plutonic rocks. This analysis strengthens the proposal that silicate melt immiscibility can be important in volcanic rocks of various compositions (from tholeiitic basalts to lamprophyres). However, the majority of proposed immiscible compositions in plutonic rocks are at least not coexisting melts, but may have suffered accumulation of early crystallized minerals.     

PT-diagram of the system SiO2-H2O

The high-temperature and medium-pressure part of the PT-diagram of the system SiO₂-H₂O has been investigated experimentally. The equilibrium diagram is discussed in the light of Schreinemakers general theory of PT-diagrams. The triple invariant point cristobalite + tridymite + quartz lies at 1190°C and 1430 atm. Neither cristobalite nor tridymite are stable at high pressure. Quartz may precipitate from the melt at a very high temperature (1360°C and higher), if the pressure is great enough, and if the water content is low. Using new experimental and published data a PT-diagram of the system SiO₂-H₂O in the large PT-region is given.     

Calorimetric study of olivine solid solutions in the system Mg2SiO4-Fe2SiO4

Solution enthalpies of synthetic olivine solid solutions in the system Mg₂SiO₄-Fe₂SiO₄ have been measured in molten 2PbO·B₂O₃ at 979 K. The enthalpy data show that olivine solid solutions have a positive enthalpy of mixing and the deviation from ideality is approximated as symmetric with respect to composition, in contrast to the previous study. Applying the symmetric regular solution model to the present enthalpy data, the interaction parameter of ethalpy (W_H) is estimated to be 5.3±1.7 kJ/mol (one cation site basis). Using this W_h and the published data on excess free energy of mixing, the nonideal parameter of entropy (W_s) of olivine solid solutions is estimated as 0.6±1.5 J/mol·K.     

Electrical conduction of Co2SiO4

This paper reports measurements of electrical conductivity in Co₂SiO₄ as a function of temperature in the range from 780 to 1540 K and oxygen fugacity in the range from 5 × 10^–8 to 2.6 × 10^–5 MPa at 1540 K. From the present data and available literature data on defect concentrations in Co₂SiO₄, the mobility of the defect responsible for conduction is determined to be 8.6 × 10^–7 m²/V-s at 1373 K. On the basis of these data and the observed dependence of conduction on oxygen fugacity, it is concluded that small polarons associated with oxidized cobalt ions is the likely mechanism controlling conduction. The mobility of small polarons in iron-bearing olivine under similar conditions is likely to be of the same order of magnitude.     

The disproportionation of andalusite (Al2SiO5) to Al2O3 and SiO2 under shock compression

Shock-recovery experiments have been carried out on andalusite single crystals of gem quality in a pressure range from 300 up to 575 kbar. Infrared spectroscopic investigations indicate a progressive shock-induced transformation of andalusite into short-range-ordered Al₂O₃ and SiO₂ phases within a pressure interval from ～360 to ～575 kbar. Exposure to dynamic pressures of about 575 kbar results in andalusite breaking down into incoherently crystallized γ-Al₂O₃, well-crystallized α-Al₂O₃ and X-ray amorphous SiO₂. The shock disproportionation of andalusite is presumed to take place in three separate stages of reaction. The comparison of shock-induced reactions with results from static experiments on kyanite indicates significant differences in the transformation pressures and in the mechanism of the high pressure decomposition.     

Infrared vibrational spectra of Beta-Phase Mg2SiO4 and Co2SiO4 to Pressures of 27 GPa

Infrared absorption spectra of the high-pressure polymorphs β-Mg₂SiO₄ and β-Co₂SiO₄ have been measured between 0 and 27 GPa at room temperature. Grüneisen parameters determined for 11 modes of β-Mg₂SiO₄ (frequencies of 300 to 1,050 cm^?1) and 5 modes of β-Co₂SiO₄ (490 to 1,050 cm^?1) range between 0.8 and 1.9. Averaging the mid-infrared spectroscopic data for β-Mg₂SiO₄ yields an average Grüneisen parameter of 1.3 (±0.1), in good agreement with the high-temperature thermodynamic value of 1.35. Similarly, we find a value of 1.05 (±0.2) for the average spectroscopic Grüneisen parameter of β-Co₂SiO₄.     

A TEM investigation of natural metamict zircons: structure and recovery of amorphous domains

The nature of the amorphous regions and their recovery processes in two natural metamict zircon samples from Sri Lanka have been studied by high resolution and analytical transmission electron microscopy. Samples untreated and annealed at different temperatures were investigated. Nanoprobe analyses on untreated samples and samples annealed at 1000 K show that within experimental uncertainties, no chemical segregation occurred. In samples annealed at higher temperatures (≥1100 K) recovery occurs in a two-stage process and leads to different microstructures, which depended on the initial amount of metamictization. In highly amorphized samples, recrystallization starts at 1200 K. Randomly oriented ZrO₂ grains embedded in a silica-rich matrix are detected. At higher temperature (16 h at 1600 K), the assemblage transforms into a polygonal texture of small zircon grains. Some untransformed zirconia grains and pockets of silica-rich glass are still present, however. In partially metamict samples, recovery starts at 1100 K. The small surviving oriented zircon domains grow at the expense of the surrounding amorphous material. At 1200 K, new zirconia grains nucleate with random orientations. After 1 h annealing at 1400 K, the zircon structure is restored and the microstructure coarse-grained. The proportion of crystalline zirconia and silica-rich glass has dramatically decreased. Received: 15 November 1999 / Accepted: 1 March 2000     

Calibration of the garnet–biotite–Al2SiO5–quartz geobarometer for metapelites

A garnet–biotite–Al₂SiO₅–quartz (GBAQ) geobarometer was empirically calibrated using more than 700 natural metapelites with a broad compositional range of garnet and biotite under P–T conditions of 450–950°C and 1–17 kbar. In the calibration, activity models of garnet and biotite identical to those in the garnet–biotite (GB) geothermometer of Holdaway [American Mineralogist 2000, 85: 881–892] were used. Therefore, the GBAQ geobarometer and the GB geothermometer can be simultaneously applied to iteratively estimate metamorphic P–T conditions. Successful applications of the GBAQ geobarometer to natural metapelites certify its validity. Most importantly, when plagioclase is absent or CaO components in garnet and/or plagioclase are deficient, this geobarometer may prove useful for estimating metamorphic pressures. The random error of the present GBAQ geobarometer is inferred to be around ±1.8 kbar. An electronic spreadsheet is available as Table S4 to apply the GBAQ geobarometer in combination with the GB geothermometer.     

Single-crystal infrared reflectivity of pure Mg2SiO2 forsterite and (Mg0.86,Fe0.14)2SiO4 olivine

New polarized infrared reflectance spectra of pure synthetic forsterite and natural Fo₈₆-olivine have been recorded from 5000 to 100cm^-1. Out of the 35 expected infrared active modes, 33 have been observed (8 B_1u, 12 B_2u, 13 B_3u). The observed frequency shift from pure forsterite to Fo₈₆-olivine is consistent with the higher mass of the substituted iron. The substitution of only 14% of iron also reduces the overal far-infrared reflectivity of olivine as compared to pure forsterite. Several discrepancies associated with previous studies of forsterite are explained by our investigation. We suggest that some of the previous investigations were complicated by polarization mixing.     

Application of empirical ionic models to SiO2 liquid: Potential model approximations and integration of SiO2 polymorph data

Structural and thermodynamic properties of crystalline SiO₂ and SiO₂ liquid have been examined with Monte Carlo (MC), molecular dynamics (MD), and energy minimization (EM) calculations using several ionic potential models obtained from the literature. The MC and MD methods calculate the same structural and thermodynamic properties for liquids when the same potential model is used. The Ewald (1921) method of calculating coulomb interactions reproduced most successfully the structure of liquid silica. Approximating the coulomb interaction by eliminating the inverse lattice sum results in predicted bond distances that are too short and an average 〈Si-O-Si〉 angle of approximately 180°. Introduction of a cut-off in the potential energy function produces irregular tetrahedra and inconsistencies in predicted Si-O coordination in silica liquid. The system internal energies show that liquid structures derived from random starting configurations can be metastable relative to structures calculated from crystalline starting configurations.The static lattice properties of the polymorphs alpha-quartz, coesite, and stishovite were used to evaluate further the accuracy of different sets of repulsive parameters for the full Ewald ionic model. Most of the models studied reproduced poorly the measured structures and elastic constants of the polymorphs. The major weakness of the ionic model is the unreasonably large Si-O bond strength (120 × 10⁻¹² ergs/bond) when formal ionic charges are used. Fractional charge models with a small Si-O bond strength (30 × 10⁻¹² ergs/bond) improve the agreement with experimental data. However, further improvement of the ionic model should include reducing the Si-O bond strength to values in better agreement with published estimates (7 × 10^{− 12} to 13 × 10⁻¹² ergs/bond). By using additional information to constrain the parameterization of the ionic model, such as estimated bond strengths and static properties of the silica polymorphs, a model more representative of the interparticle interactions may be obtained.     

Crystal structures of Ni2SiO4 and Fe2SiO4 as a function of temperature and heating duration

X-ray structure refinements of Ni₂SiO₄ and Fe₂SiO₄ spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni₂SiO₄ spinel linearly increased with temperature up to 1,000° C. However, Fe₂SiO₄ spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D _oct/D _tetr and between the shared and unshared edge distances (O-O)_sh/(O-O)_unsh in Fe₂SiO₄ spinel were both much larger than those in Ni₂SiO₄. These ratios increase with temperature. The Fe₂SiO₄ spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni₂SiO₄ spinel. The lattice parameter of Ni₂SiO₄ spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal.     

水泥-水玻璃浆材在灌浆工程中的应用

水泥-水玻璃作为一种复合型灌浆材料,集中了水泥和水玻璃两种灌浆材料的优点,在许多灌浆工程中发挥了重要作用。本文从水泥、水玻璃的基本性能出发,对水泥-水玻璃灌浆材料的性能和应用进行了探讨