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1.
Crystals of sodium trisilicate (Na2Si3O7) have been grown in the presence of melt at 9 GPa, 1200 °C using the MA6/8 superpress at Edmonton, and the X-ray structure determined at room pressure (R=2.0%). Na2Si3O7 is monoclinic with a=8.922(2) Å, b= 4.8490(5) Å, c=11.567(1) Å, β=102.64(1)° (C2/c), D x = 3.295 g·cm-3. Silicon occurs in both tetrahedral and octahedral coordination ([6]Si∶[4]Si = l∶2). The SiO4 tetrahedra form a diorthosilicate [Si2O7] group and are linked by the isolated SiO6 octahedra via shared corners into a framework of 6-membered ([4]Si-[4]Si-[6]Si[4]Si-[4] Si-[6]Si) and 4-membered ([4]Si-[6]Si-[4]Sr-[6]Si) rings: 〈[6]Si-O〉=1.789 Å, 〈[4]Si-O〉= 1.625 Å, [4]Si-O-[4]Si=132.9° and the bridging oxygen is overbonded (s = 2.22). Channels parallel to b-axis and [110] accommodate Na in irregular 6-fold coordination: 〈Na-O〉 = 2.511 Å.  相似文献   

2.
Eifelite of variable composition is uniaxial positive withn 0 near 1.543 andn e near 1.544, a between 10.14 and 10.15 Å, andc about 14.22 Å, space groupP 6/m 2/c 2/c. There is a complete series of solid solution between the eifelite end member KNa3Mg4Si12O30 and roedderite, KNaMg5Si12O30, following the 2 Na?Mg substitution. Both eifelite and roedderite have milarite-type structures, but Na is always in six-coordinated sites: In roedderite Na occupies solely a newly defined B′[6]-position which is slightly displaced alongc from the ideal B[9]-position lying on the (001/2)-mirror plane in K2Mg5Si12O30. In eifelite Na is located both inB′[6] and in theA [6]-positions, where it partially replaces Mg. Eifelite has the highest cation occupancy of all osumilite group minerals known thus far. Both eifelite and roedderite occur in vesicles of contact metamorphosed basement xenoliths ejected with the leucite tephrite lava of the Quaternary Bellerberg volcano in the Eifel, West Germany. They are considered to be precipitates from highly alkaline, MgSi-rich, but Al-deficient gas phases that originated through interaction of gaseous igneous differentiates with the xenoliths.  相似文献   

3.
 Amphiboles were synthesized from bulk compositions prepared along the join Ca1.8Mg5.2Si8O22(OH)2–Ca1.8Mg3Ga4Si6O22(OH)2 hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca2Mg5Si8O22F2–Ca2Mg3Ga4Si6O22F2, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: [6]Ga3++2[4]Ga3++1/2[A] Ca2+ = [6]Mg2++2[4]Si4++1/2[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001  相似文献   

4.
The mineral chemistry of cordierites from three different sanidinite facies localities-1) volcanic xenoliths from the Eifel, Germany; 1) buchites of the Blaue Kuppe, Germany; 3) paralavas from the Bokaro coalfield, India-is characterized by unusually high potassium contents up to 1.71 wt%, equivalent to 0.22 K atoms per formula unit (p.f.u.) based on 18 oxygens. Significantly, these cordierites are either hexagonal highcordierites (indialites) with =0 or exhibit intermediate -values 0<<0.20 relative to well Al,Si-ordered orthorhombic low-cordierite. Based on microprobe analyses, the predominant substitutional mechanism for alkali incorporation is Alk[Channel]+Al[4] for +Si[4], thus leading to Al/Si-ratios deviating considerably from the value 4:5 in ideal cordierite M2[Al4Si5O18]. The most highly substituted cordierite from Blaue Kuppe is about (K0.22Na0.07)[Ch](Mg1.33Fe 0.66 2+ )[6][Al4.16Si4.79O18]. Bokaro cordierites are further characterized by obvious (Al+Si)-deficiencies against the ideal value of 9.0 p.f.u., a tendency of which is apparent in most Blaue Kuppe analyses as well. As the tetrahedral deficiencies are often equivalent to excess cations in the octahedra, we assume that ferric iron fills up the remaining tetrahedral sites, again linked with the introduction of potassium according to K+Fe3+ for +Si. In comparison with the available experimental data, these natural potassic cordierites are considered stable high-temperature phases regarding their compositions, but not their structural states. Although the substitution KAl for Si in Mg-cordierite is known to lower the maximum -value to be attained, the hexagonal nature of the cordierites must be due to very rapid crystallization and subsequent quenching. The higher -values of the Blaue Kuppe cordierites might be caused by their topotactic origin from preexisting biotite. The complicated twin and domain patterns of the hexagonal Eifel and Bokaro cordierites as observed in thin section could perhaps be attributed to structural modulations as postulated recently for hexagonal cordierite shortly after its growth.  相似文献   

5.
Friedrichbeckeite is a new milarite-type mineral. It was found in a single silicate-rich xenolith from a quarry at the Bellerberg volcano near Ettringen, eastern Eifel volcanic area, Germany. It forms thin tabular crystals flattened on {0001}, with a maximum diameter of 0.6 mm and a maximum thickness of 0.1 mm. It is associated with quartz, tridymite, augite, sanidine, magnesiohornblende, enstatite, pyrope, fluorapatite, hematite, braunite and roedderite. Friedrichbeckeite is light yellow, with white to light cream streak and vitreous lustre. It is brittle with irregular fracture and no cleavage, Mohs hardness of 6, calculated density is 2.686 gcm?3. Optically, it is uniaxial positive with nω = 1.552(2) and nε = 1.561(2) at 589.3 nm and a distinct pleochroism from yellow (//ω) to light blue (//ε). Electron microprobe analyses yielded (wt.%): Na2O 2.73, K2O 4.16, BeO 4.67, MgO 11.24, MnO 2.05, FeO 1.76, Al2O3 0.15, SiO2 73.51, (Σ CaO, TiO2 = 0.06) sum 100.33 (BeO determined by LA-ICP-MS). The empirical formula based on Si = 12 is K0.87 Na0.86 (Mg1.57Mn0.28Fe0.24)Σ2.09 (Be1.83?Mg1.17)Σ3.00 [Si12O30], and the simplified formula can be given as K (□0.5Na0.5)2 (Mg0.8Mn0.1Fe0.1)2 (Be0.6?Mg0.4)3 [Si12O30]. Friedrichbeckeite is hexagonal, space-group P6/mcc, with a = 9.970(1), c = 14.130(3) Å, V = 1216.4(3) Å3, and Z = 2. The strongest lines in the X-ray powder diffraction pattern are (d in Å / I obs / hkl): 3.180 / 100 / 121, 2.885 / 70 / 114, 4.993 / 30 / 110, 4.081 / 30 / 112, 3.690 / 30 / 022. A single-crystal structure refinement (R1 = 3.62 %) confirmed that the structure is isotypic with milarite and related [12] C [9] B 2 [6] A 2 [4] T23 [[4] T112O30] compounds. The C-site is dominated by potassium, the B-site is almost half occupied by sodium, and the A-site is dominated by Mg. The site-scattering at the T2-site can be refined to a Be/(Be?+?Mg) value close to 0.61; the T1-site is occupied by Si. Micro-Raman spectroscopy reveals an increasing splitting of scattering bands around 550 cm?1 for friedrichbeckeite. The mineral can be classified as an unbranched ring silicate or as a beryllo-magnesiosilicate. With respect to the end-member formula K (□0.5Na0.5)2 Mg2 Be3 [Si12O30] friedrichbeckeite represents the Mg-dominant analogue of almarudite, milarite or oftedalite. The mineral and its paragenesis were formed during pyrometamorphic modifications of the silicate-rich xenoliths enclosed in Quaternary leucite-tephritic lava of the Bellerberg volcano. Holotype material of friedrichbeckeite has been deposited at the mineral collection of the Naturhistorisches Museum Wien, Austria. The mineral is named friedrichbeckeite in honour of the Austrian mineralogist and petrographer Friedrich Johann Karl Becke (1855–1931).  相似文献   

6.
Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1–0.5 GPa and 200–850 °C for durations of 18–1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg10Si12O32(OH)4), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na4Mg8Si12O32(OH)4. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO2, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F− for OH−, Mn2+, Ca2+, or Fe2+ for Mg2+, and 2Li+ for Mg2+ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440–630 °C and 0.2 GPa from the composition Na4Mg8Si12O32(OH)4, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na4Mg8Si12O32F4 at 550–750 °C and 0.2–0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na+ for Na+ + H+ and of Mg2+ + vacancy for 2Na+. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na2.5Mg8Si12O30.5(OH)5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na1.1Mg9.4Si12O31.9(OH)4.1 based on a fixed number of Si cations. Further investigation involving Mg for Na cation exchange may provide a pathway for the synthesis of Na-free clinojimthompsonite. Fairly extensive solid solution was also observed for triple-chain silicates made along the compositional join Na4Mg8Si12O32(OH)4–Ca2Mg8Si12O32(OH)4 where the limit of Ca substitution at 450 °C and 0.2 GPa corresponds to Na0.7Ca1.8Mg7.8Si12O31.9(OH)4.1 (with the OH content adjusted to achieve charge balance). Aside from the Na content, this composition is similar to that observed as wide-chain lamellae in host actinolite. The relative ease with which Na-rich triple chains can be made experimentally suggests that these phases might exist in nature; this study provides additional insights into the range of compositions and formation conditions at which they might occur.  相似文献   

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

8.
 Nuclear reaction analyses on boron in flux-grown Me3+- and Na+-doped diopside crystals utilising the 11B(p,2α)4He reaction in conjunction with EMP analyses for major elements and optical absorption spectroscopy for determination of Me-valence state distributions show that appreciable amounts of B may enter the diopside lattice in crystals produced in Na2B4O7 fluxes. The results indicate that the substitution [6]Me3+[4]B3+[6]Mg2+ −1 [4]Si4+ −1 operates in the present diopside samples in addition to the coupled substitution [6]Me3+[8]Na+[6]Mg2+ −1 [8]Ca2+ −1. The specific NRA technique applied allows for quantitative, high resolution (ca. 5 μm) B analyses at ppm level as well as high-resolution and high-contrast imaging of B-concentration patterns in minerals. The estimated detection limit and relative error of the B analyses are 10 ppm and 5–10%, respectively. Received: 20 September 1999 / Accepted: 6 June 2000  相似文献   

9.
Single crystals of C–Na2Si2O5 have been synthesized from the hydrothermal recrystallization of a glass. The title compound is monoclinic, space group P21/c with Z= 8 and unit-cell parameters a= 4.8521 (4)Å, b=23.9793(16)Å, c=8.1410(6)Å, β=90.15(1)° and V=947.2(2)Å3. The structure has been determined by direct methods and belongs to the group of phyllosilicates. It is based on layers of tetrahedra with elliptically six-membered rings in chair conformation. The sequence of directedness within a single ring is UDUDUD. The sheets are parallel to (010) with linking sodium cations in five- and sixfold coordination. Concerning the shape and the conformation of the rings, C–Na2Si2O5 is closely related to β-Na2Si2O5. However, both structures differ in the stacking sequences of the layers. A possible explanation for the frequently observed polysynthetic twinning of phase C is presented. In the 29Si MAS-NMR spectrum of C–Na2Si2O5 four well-resolved lines of equal intensity are observed at ?86.0, ?86.3, ?87.4, and ?88.2?ppm. The narrow range of isotropic chemical shifts reflects the great similarity of the environments of the different Si sites. This lack of pronounced differences in geometry renders a reliable assignment of the resonance lines to the individual sites on the basis of known empiric correlations and geometrical features impossible.  相似文献   

10.
Fluoro-sodalite was synthesized for the first time at temperatures of 400–800°C and H2O pressures of 1–2 kbar in the Si–Al–Na–H–O–F system. X-ray diffraction and infrared spectroscopic investigations showed that fluorine is incorporated in the sodalite structure as anionic octahedral groups, [AlF6]3–, the number of which can vary from 0 to 1. Correspondingly, the end-members of the F-sodalite series are Na7(H2O)8[Si5Al7O24] and Na8(AlF6)(H2O)4[Si7Al5O24]. Depending on the composition of the system, F-sodalite associates at 500–650°C with nepheline, albite, cryolite, and villiaumite, which are joined by analcime below 500°C and aluminosilicate melt above 650°C. Fluorine-bearing sulfate–chlorine-sodalite was found for the first time in a pegmatite sample from the Lovozero massif. The highest fraction of the fluorine end-member in natural sodalite is 0.2. The incorporation of F into the sodalite structure requires much more energy compared with Cl– and SO 4 2- , because it is accompanied by a structural rearrangement and a transition from tetrahedral Al to octahedral Al.  相似文献   

11.
The Lovozero pluton (Kola Peninsula, Russia) is an unique object from the standpoint of the abundance, diversity, and originality of Th mineralization. In contrast to other igneous rocks and to such chemical elements as Ca, REE, U, and Na, Th in the hyperalkaline pegmatites and hydrothermalites of the Lovozero pluton commonly occurs as its own mineral phases. Umbozerite Na3Sr4Th(Mn,Zn,Fe,Mg)[Si8O24](OH) (7 samples), Ti-Th silicate Na0–7Sr0–1ThTi1–2Si8O22–23(OH) · nH2O (8 samples), Na-Th silicate (Na,K)4Th3[Si8(O,OH)24] · nH2O (6 samples), thorite (2 samples), steenstrupine-(Ce)-thorosteenstrupine series minerals (5 samples), and Th phosphate (Th,Na,K,Ca,Mg,U,Sr,Ba)[(P,Si, Al)1O4] · nH2O (1 sample) were investigated in this study. Ti-Th silicates and Th phosphate have been described for the first time. All of the above-mentioned minerals have been examined with electron microprobe, IR spectroscopy, powder diffraction, thermogravimetric and optical methods. High-Th minerals such as steenstrupine, umbozerite, Th phosphate, and Na-Th silicates crystallized mainly during the ussingite stage of the pegmatite-forming process. At the early hydrothermal high-alkaline stage, steenstrupine was replaced with REE and Th aggregates (belovite, vitusite, seidite, Na-Th silicates, Ti-Th silicates, etc.). Thorite, Ti-Th silicates, and minerals of the rhabdophane and monazite groups were formed at the late hydrothermal low-alkaline stage. Despite the metamict features of almost all samples, stoichiometric ratios of cations in umbozerites and Ti-Th silicates remain stable. Clear relationships have been revealed between umbozerites and Ti-Th silicates, on the one hand, and seidite-(Ce), a Ti-silicate that has a zeolite-like structure, on the other. This implies that, under certain conditions, these minerals may be regarded as potential suppliers of Th to the environment due to the leaching of Th from zeolite channels.  相似文献   

12.
Natural nepheline, a synthetic Na-rich nepheline, and synthetic kalsilite were ion exchanged in molten MNO3 or MCl (M = Li, Na, K, Ag) at 220–800° C. Crystalline products were characterized by wet chemical and electron microprobe analysis, single crystal and powder X-ray diffraction, and transmission electron microscopy and diffraction. Two new compounds were obtained: Li-exchanged nepheline with a formula near (Li,K0.3,□)Li3[Al3(Al,Si)Si4O16] and a monoclinic unit cell with a = 951.0(6) b = 976.1(6) c = 822.9(5)pm γ = 119.15°, and Ag-exchanged nepheline with a formula near (K,Na,□)Ag3[Al3(Al,Si)Si4O16] and a hexagonal unit cell with a = 1007.4(8) c = 838.2(1.0) pm. Both compounds apparently retain the framework topology of the starting material. Ion exchange isotherms and structural data show that immiscibility between the end members is a general feature in the systems Na-Li, Na-Ag, and Na-K. For the system Na-K, a stepwise exchange is observed with (K,D)Na3[Al3(Al,Si)Si4O16] as an intermediate composition which has the nepheline structure and is miscible with the sodian end member (Na,□)Na3[Al3(Al,Si)Si4O16], but not with the potassian end member (K,□)4[Al3(Al,Si)Si4O16] which shows the kalsilite structure; there was no indication for the formation of trior tetrakalsilite (K/(K + Na)≈0.7) at the temperatures studied (350 and 800° C). The exact amount of vacancies □ on the alkali site depends upon the starting material and was found to be conserved during exchange, with ca 0–0.2 and 0.3–0.4 vacancies per 16 oxygen atoms for the synthetic and natural precursors, respectively. Thermodynamic interpretation of the Na-K exchange isotherms shows, as one important result, that the sodian end member is unstable with respect to the intermediate at K/(K+Na)≈0.25 by an amount of ca 45 kJ/mol Na in the large cavity at 800° C (52 kJ/mol at 350° C).  相似文献   

13.
The solubility of Tio2 in phlogopites has been experimentally determined in the system K2Mg6Al2Si6O20(OH)4-K2Mg4TiAl2Si6O20(OH)4-K2Mg5TiAl4Si4O20(OH)4 between 825–1300°C and 10–30 kbar under vapour absent conditions. Starting compositions lie along the join K2Mg6Al2Si6O20(OH)4-K2Mg4.5TiAl3Si5O20(OH)4 which represents a combination of the Mg[VI]2Si[IV] = Ti[VI]2Al[VI] and 2Mg[VI] = Ti[VI]□[VI] substitution mechanisms for Ti in phlogopites. The results of the experiments indicate a systematic increase in solubility of Ti with increasing temperature and decreasing pressure for given bulk Tio2 content. Under isobaric conditions high temperature Ti-saturated phlogopite breaks down to Ti-deficient phlogopite + rutile + vapour. Mass balance calculations suggest that the vapour phase may contain K2O dissolved in H2O and that the reaction is controlled by the vapour phase. Analyses of phlogopites coexisting with rutile and vapour can be represented in terms of the end-member components phlogopite [K2Mg6Al2Si6O20(OH)4], eastonite [K2Mg5Al4Si5O20(OH)4], an octahedral site deficient Ti-phlogopite (Ti-OSD) of composition K2(Mg4Ti□)Al2Si6)O20(OH)4, and Ti-eastonite [K2Mg5TiAl4Si4O20(OH)4]. With decreasing amounts of Ti in these phlogopites there is a decrease in the Ti-eastonite component and increase in the eastonite component.The general equation for the breakdown of Ti-phlogopite solid solution to Ti-free phlogopite + rutile + vapour is: 14 Ti-eastonite + 7 Ti-OSD ? 16 eastonite + 3 phlogopite + 21 rutile + 4 H2O + 2 K2O. Lack of knowledge of H2O and K2O activities in the vapour phase does not permit evaluation of thermodynamic constants for this reaction. The Ti solubility in phlogopites and hence its potential as a geothermobarometer under lower crustal to upper mantle conditions is likely controlled by common mantle minerals such as forsterite.  相似文献   

14.
Ab initio, molecular orbital calculations at the 3–21G* level were carried out on H6Si3O9, [H6Si2AlO2]1?, [H6SiAl2O9]2?, and [H6A13O9]3? cyclic molecules in order to determine their structures and vibrational frequencies. These three-membered rings were found to have minima in their potential energy surfaces indicating stability of the species. The H6Si3O9 ring was found to be slightly non-planar, but the [H6SiAl2O9]2? and [H6Al33O9]3? configurations are more planar. Vibrational frequencies of the Raman-active, bridging oxygen “breathing” modes increase with Si4+ content. Galeener's (1982a, b) assignment of the D2 peak (606 cm?1) in the Raman spectrum of vitreous silica to an oxygen breathing mode in rings of three SiO4 tetrahedra is reconfirmed. Correlation of the ring breathing mode frequencies as a function of (AI/AI + Si) with Raman peaks in the SiO2-NaAlSiO4 system is high. Three-membered aluminosilicate rings are likely to exist and give rise to Raman peaks between 540 and 600 cm?1 in fully-polymerized aluminosilicate glasses.  相似文献   

15.
The coordination environment of Fe(II) has been examined in seven anhydrous ferrosilicate glasses at 298 K and 1 bar using 57Fe Mössbauer, Fe K-edge X-ray near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS), UV-Vis-NIR, and magnetic circular dichroism (MCD) spectroscopies. Glasses of the following compositions were synthesized from oxide melts (abbreviation and nonbridging oxygen:tetrahedral cation ratio (NBO/T) in parentheses): Li2FeSi3O8 (LI2: 1.33), Rb2FeSi3O8 (RB2: 1.33), Nal.08Fel.l7Si3.l3O8 (NAl: 1.09), Nal.46Ca0.24Fel.08Si2.97O8 (NC6: 1.38), Nal.09Ca0.51Fe0.72Si3.10O8 (NC2: 1.15), Na0.99Ca0.92Fe0.24 Si3.17O8 (NCl: 1.04), and Na0.29Mg0.53Ca0.52Fe0.56Al0.91Si2.44O8 (BAS: 1.05). Mössbauer, XANES, and EXAFS information suggests that iron is dominantly ferrous in all glasses (<10 atom% Fe(III)) with an average first-neighbor Fe(II) coordination varying from ∼ 4 to 5.2 (±0.2) oxygens. The UV-Vis-NIR spectrum of each sample exhibits intense absorption centered near 8100-9200 cm−1 and weak absorption near 5000 cm−l, which cannot be assigned unambiguously. The MCD spectrum of NC6 glass, which is the first such measurement on a silicate glass, shows three transitions at ∼8500 cm−1, ∼6700 cm−1, and ∼4500 cm−1. The behavior of these MCD bands as a function of temperature (1.6 K to 300 K) and magnetic field strength (1 T to 7 T) indicates that they most likely arise from three distinct Fe(II) sites with different ground states, two of which are 5-coordinated and one of which is 4-coordinated by oxygens.The combined results suggest that Fe(II) predominantly occupies 5- and 4-coordinated sites in each glass, with the ratios differing for the different compositions. Small amounts of 6-coordinated Fe(II) are possible as well, but primarily in the more basic glass compositions such as BAS. The substitution of Li(I) for Rb(I) in the M2FeSi3O8 base glass composition causes a weakening of the average Fe(II)-O bond, as indicated by the longer Fe(II)-O distance in the latter. The basalt composition glass was found to have the largest Fe(II) sites relative to those in the other glasses in this study. A bond valence model that helps predict the coordination number of Fe(II) in silicate glasses is proposed. The structural information extrapolated to Fe(II)-bearing melts is parameterized using bond valence theory, which helps to rationalize the melt-crystal partitioning behavior of ferrous iron in natural and synthetic melt-crystal systems.  相似文献   

16.
Tecto-aluminosilicate and peraluminous glasses have been prepared by conventional and laser heating techniques, respectively, in the CaO-Al2O3-SiO2 system. The structure of these glasses were studied using Raman spectroscopy, X-ray absorption at the Al K-edge and 27Al NMR spectroscopy with two different high fields (400 and 750 MHz). Raman spectroscopy and X-ray absorption are techniques sensitive to the network polymerization and, in particular, show different signal as a function of silica content. However, these two techniques are less sensitive than NMR to describe the local aluminium environment. For tectosilicate glasses, aluminium in five-fold coordination, [5]Al, was found and a careful quantification allows the determination of a significant amount of [5]Al (7% in the anorthite glass). The proportion of [5]Al increases for the peraluminous glasses with small amounts (<2%) of six-fold coordination, [6]Al. The presence of [5]Al agrees with previous observations of the existence of nonbridging oxygens (NBOs) in tectosilicate compositions. However, the proportion of [5]Al in the present study indicates that no major proportion of triclusters (oxygen coordinated to three (Si,Al)O4 tetrahedra) is required to explain these NBOS.  相似文献   

17.
Structural formulae of many Ti-rich hornblendes and biotites exhibit cation deficiencies that increase with Ti content. These deficiencies may be caused by the presence of trivalent instead of tetravalent Ti, of oxygen replacing hydroxyl, or of vacancies on octahedral cation sites. In order to determine the oxidation state of their Ti, electron energy-loss spectra of natural, Ti-rich hornblende and biotites are compared with spectra of natural and synthetic Ti-bearing oxides and silicates. Spectra of Ti2O3 and TiO2 demonstrate that the Ti L 2,3 edge for Ti3+ is shifted by ca. 2 eV to lower energy relative to the edge for Ti4+. Oxidation states of Ti determined by energy-loss spectroscopy for several minerals agree with data from other techniques: tetravalent for Ti-omphacite, perovskite, ilmenite and titanite; trivalent for NaTi3+Si2O6 pyroxene and fassaite from the Allende meteorite. The energy-loss spectra of the hornblende and biotite show that their Ti is tetravalent and cannot be the cause of the cation deficiencies. The relations between Ti contents and the number of deficiencies differ for hornblende and biotite. Hornblende shows a 2:1 relation between Ti content and deficiencies, suggesting Ti is coupled to an oxygen that is replacing hydroxyl (Ti-oxyhornblende substitution). Biotite shows a 1:1 relation, consistent with coupling of Ti to a vacant octahedral cation site (Ti-vacancy substitution) or to a variable combination of such vacancies and two oxygens replacing hydroxyls (Ti-oxybiotite substitution).  相似文献   

18.
The minerals ??hackmanite?? and tugtupite exhibit tenebrescence (reversible photochromism) and photoluminescence. These features are generally attributed to the presence of sulfide species within their structures. But how these optical properties might be affected by intercalating additional amounts of sulfur into their structures was until now unknown. Artificial ??hackmanite??, Na8[Al6Si6O24]Cl1.8S0.1, and ??sulfosodalite??, Na8[Al6Si6O24]S, were heated with sulfur in evacuated quartz-glass ampoules over the temperature range 450?C1,050°C. This work has shown that sulfur intercalation into Na8[Al6Si6O24]Cl1.8S0.1 destroys the tenebrescence and induces a permanently pale blue and, at higher temperature, a pale green coloration. The effect on Na8[Al6Si6O24]S induced similar colorations but of a deeper hue. Annealing tugtupite, Na8[Be2Al2Si8O24](Cl,S)2??? under a sulfur atmosphere over the range 600?C700°C, destroyed the tenebrescence and resulted in a colorless tugtupite; but did not effect the photoluminescence. This suggests that the chemical species responsible for the tenebrescence in tugtupite is unlikely to be the same as that for the luminescence.  相似文献   

19.
Geometrical changes induced by cation substitutions {Si4+/Al3+}[Mg2+/Al3+], {2Si4+/2Al3+} [2Mg2+/2Al3+], {Si4+/Fe3+} [Mg2+/Al3+] or [Mg2+/Fe3+], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1T and 2H 1, up to ~30% in the 2H 2 polytype. Si4+ by Fe3+ substitution in the tetrahedral sheet with an Al3+ (Fe3+) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.  相似文献   

20.
Normal coordinate calculations have been carried out on partially polymerized simple silicate crystals, including Li and Na di- and metasilicates, Li and Gd pyrosilicates, thortveitite and rankinite. In the antisymmetric Si-O stretching modes which are active at 800–1200 cm?1 in infrared spectra, Si-Obr vibrations occur at higher frequencies than Si-Onb vibrations if the bonds have equivalent strengths. However, this relationship is usually reversed when bridging oxygens are overbonded and non-bridging oxygens are underbonded in terms of Pauling bond strengths, a situation which is generally more common in crystals. An observed bimodality of the high-frequency envelope in infrared spectra of glasses in the alkali oxide-silica systems may be somewhat fortuitous, with the high frequency component (ca. 1100 cm?1) representing underbonded non-bridging oxygens and saturated bridging oxygens, and the lower-frequency component (ca. 1000 cm?1) mainly oversaturated bridging oxygens. Significant differences between crystals and glasses in the number and location of the main high-frequency infrared peaks suggest that there are short-range bonding rearrangements in the glasses, and that crystallite models are not applicable. Mid-frequency (600–800 cm?1) infrared modes in silicates more polymerized than the pyrosilicate (Si2O7) appear to be mostly antisymmetric modes in which Si rattles against bridging oxygens, rather than symmetric stretching modes.  相似文献   

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