High pressure rhombohedral perovskite phase Ca2AlSiO5.5

A new high pressure phase with the composition Ca₂AlSiO_5.5 has been synthesized using an MA-8 apparatus operating at 1700° C and 16 GPa. The phase possesses a structure analagous to CaSiO₃ perovskite but with half the Si atoms replaced by Al, and charge balance provided by vacancies in the oxygen sub-lattice. The unit cell possesses a lattice parameter, a_o = 3.706 ± 0.003 Å (room P and T value), based on a simple cubic perovskite structure. However, electron diffraction shows that a superstructure has developed parallel to one of the {111} cubic planes with a wavelength of 10.70 Å (equals 5 × ¦d₁₁₁¦), so that the Ca₂AlSiO_5.5 cell must be described formally as rhombohedral with a = 11.12 Å and = 27.27 degrees. This rhombohedral cell is metrically cubic, since the distortion of the cubic cell is not determinable from X-ray diffraction patterns obtained so far. The calculated density of this high pressure phase Ca₂AlSiO_5.5 is 3.64 gm·cm^-3. This low density is related in part to the large proportion of oxygen vacancies present in the structure. Because of the low density, this phase is unlikely to be a significant mineralogical constituent of the lower mantle, unless the phase is characterized by extreme compressibility. However, the identification of the phase may be of significance in showing how A1₂O₃ can be accommodated in silicate perovskite via replacement of Si^VI in octahedral sites accompanied by production of one oxygen defect for every 2 Al atoms substituted. The possibility that this mode of substitution might be relevant to the incorporation of Al₂O₃ in MgSiO₃ perovskite warrants further study.     

High pressure elasticity and phase transformation in brucite, Mg(OH)2

The first pressure derivatives of the second-order elastic constants have been calculated for brucite, Mg(OH)₂ from the second- and third-order elastic constants. The deformation theory and finite strain elasticity theory have been used to obtain the second- and third-order elastic constants of Mg(OH)₂ from the strain energy of the lattice. The strain energy ϕ is calculated by taking into account the interactions up to third nearest neighbors in the Mg(OH)₂ lattice. ϕ is then compared with the strain dependent lattice energy from continuum model approximation to obtain the expressions of elastic constants. The complete set of six second-order elastic constants C _IJ of brucite exhibits large anisotropy. Since C ₃₃ (= 21.6 GPa), which corresponds to the strength of the material along the c-axis direction, is less than the longitudinal mode C ₁₁ (= 156.7 GPa), the interlayer binding forces are weaker than the binding forces along the basal plane of Mg(OH)₂. The 14 nonvanishing components of the third-order elastic constants, C _IJK , of brucite have been obtained. All the C _IJK of brucite are negative except the values of C ₁₁₄ (= 230.36 GPa), C ₁₂₄ (= 75.45 GPa) and C ₁₃₄ (= 36.98 GPa). The absolute values of the C _IJK are, in general, one order of magnitude greater than the C _IJ ’s in the Mg(OH)₂ system as usually expected for a crystalline material. To our knowledge, no previous data are available to compare the pressure derivatives of brucite. The pressure derivatives of the two components viz., C ₁₄ and C ₃₃ become negative indicating an elastic instability in brucite while under pressure. This may be related to the phase transition of brucite largely involving rearrangements of H atoms revealed in the Raman spectroscopic, powder neutron diffraction and synchrotron X-ray diffraction studies.     

The low-pressure stability of phase A,Mg7Si2O8(OH)6

 Phase A, Mg₇Si₂O₈(OH)₆, is a dense hydrous magnesium silicate whose importance as a host of H₂O in the Earth’s mantle is a subject of debate. We have investigated the low-pressure stability of phase A in experiments on the reaction phase A=brucite+forsterite. Experiments were conducted in piston-cylinder and multi-anvil apparatus, using mixtures of synthetic phase A, brucite and forsterite. The reaction was bracketed between 2.60 and 2.75 GPa at 500° C, between 3.25 and 3.48 GPa at 600° C and between 3.75 and 3.95 GPa at 650^° C. These pressures are much lower than observed in the synthesis experiments of Yamamoto and Akimoto (1977). At 750^° C the stability field of brucite + chondrodite was entered. The enthalpy of formation and entropy of phase A at 1 bar (10⁵ Pa), 298 K, were derived from the experimental brackets on the reaction phase A=brucite+forsterite using a modified version of the thermodynamic dataset THERMOCALC of Holland and Powell (1990), which includes a new equation of state of H₂O derived from the molecular dynamics simulations of Brodholt and Wood (1993). The data for phase A are: ΔH ^o _f =−7126±8 kJ mol^-1, S ^o=351 J K^-1 mol^-1. Incorporating these data into THERMOCALC allows the positions of other reactions involving phase A to be calculated, for example the reaction phase A + enstatite=forsterite+vapour, which limits the stability of phase A in equilibrium with enstatite. The calculated position of this reaction (753° C at 7 GPa to 937° C at 10 GPa) is in excellent agreement with the experimental brackets of Luth (1995) between 7 and 10 GPa, supporting the choice of equation of state of H₂O used in THERMOCALC. Comparison of our results with calculated P-T paths of subducting slabs (Peacock et al. 1994) suggests that, in the system MgO–SiO₂–H₂O, phase A could crystallise in compositions with Mg/Si>2 at pressures as low as 3 GPa. In less Mg rich compositions phase A could crystallise at pressures above approximately 6 GPa. Received: 3 July 1995/Accepted: 14 December 1995     

Bearthite,Ca2Al(PO4)2OH: stability,thermodynamic properties and phase relations

Contributions to Mineralogy and Petrology - The new phosphate bearthite, Ca2Al(PO4)2HO, found in high-pressure metamorphic rocks, has been synthesized from a stoichiometric mixture of γ-Al2O3...     

Slope stability analysis in 3D using numerical limit analysis (NLA) and elasto-plastic analysis (EPA)

The present paper addresses the problem of factor of safety (FS) determination in 3D slope stability analysis. For that purpose, use is made of two numerical methods/techniques in three benchmark problems: numerical limit analysis (NLA) and elasto-plastic analysis (EPA). Finite elements are used in both techniques. The primary objective of the study is, by comparing the two techniques, to establish the feasibility of using NLA in the evaluation of 3D slope stability problems and to establish its practical applicability and competitiveness in relation to EPA. Because of their geometry or their boundary conditions, the problems cannot be analysed as plane strain state problems or using the 2D limit equilibrium technique. In both methods, an FS is determined for the slopes by reducing the strength parameters of the geological materials using a scalar factor, known as the strength reduction factor. From the comparison of the FSs and of the computational efforts required for the two numerical techniques, it was possible to establish NLA’s competiveness and viability for the analysis of real 3D slope stability problems when implemented in an efficient manner.     

The crystal structure of trigonite,Pb3Mn(AsO3)2(AsO2OH)

Summary The mineral trigonite crystallizes in the monoclinic space groupPn–C _s ² witha ₀=7.26,b ₀=6.78,c ₀=11.09Å; =91.5°,Z=2. The structure was determined from 1250 X-ray intensities collected on an automatic two circle Weissenberg-type diffractometer. The final residual isR=6.5% using anisotropic temperature factors for Pb, Mn and As, and isotropic temperature factors for O.The structure consists of MnO₆ octahedra, sharing all six oxygens with arsenite groups to form a framework. The Pb atoms are attached to this framework with Pb–O distances2.23Å. One oxygen, bound only to an As atom, is interpreted as the donor for a hydrogen bond of 2.75Å.

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Die Kristallstruktur des Trigonits, Pb₃Mn(AsO₃)₂(AsO₂OH)

Zusammenfassung Das Mineral Trigonit kristallisiert monoklin, RaumgruppePn–C _s ² ,a ₀=7,26,b ₀=6,78,c ₀=11,09Å; =91,5°;Z=2. Die Strukturermittlung erfolgte anhand von 1250 Röntgenintensitäten, die auf einem automatischen Zweikreis-Weissenbergdiffraktometer gesammelt wurden. Mit anisotropen Temperaturfaktoren für Pb, Mn und As sowie isotropen für die O-Atome ergibt sich einR-Wert von 6,5%.Die MnO₆-Oktaeder werden über die sechs Sauerstoffe mit Arsenitgruppen zu einem dreidimensionalen Gerüst verknüpft. Über Pb-O-Abstände2,23 Å sind die Pb-Atome in dieses Gerüst eingebaut. Ein Sauerstoff, nur an ein As-Atom gebunden, wird als Donator einer H-Brücke von 2,75 Å interpretiert.

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利用尾矿砂制备镁铁氢氧化物实验研究

以金川铜镍矿尾矿酸浸液为原料,根据矿物沉淀pH值区间的不同,分步分离Fe、Mg的沉淀物以及有价金属Al、Co、Ni、Cu的混合沉淀物,进而制备具有高附加值的Fe(OH)3和Mg(OH)2,同时富集Co、Ni、Cu等有价金属。结果表明,当溶液pH值为3.8时可沉淀分离出主要成分为施威特曼石(schwertmannite)的氢氧化铁前驱体,pH值达到9.8时沉淀富集出Al、Co、Ni、Cu的混合氢氧化物,随即得到只含有Mg离子的溶液。在60℃条件下,将施威特曼石在pH值为12的NaOH溶液中老化36h,可以得到Fe(OH)3。同时,以NaOH调节只含有Mg离子的溶液至pH值为12.4时可获得Mg(OH)2。本研究为金属矿山尾矿的资源化综合利用提供了新的思路与方法。     

Single-crystal elastic properties of alunite, KAl3(SO4)2(OH)6

The single-crystal elastic constants of natural alunite (ideally KAl₃(SO₄)₂(OH)₆) were determined by Brillouin spectroscopy. Chemical analysis by electron microprobe gave a formula KAl₃(SO₄)₂(OH)₆. Single crystal X-ray diffraction refinement with R ₁ = 0.0299 for the unique observed reflections (|F _o| > 4σ _F) and wR ₂ = 0.0698 for all data gave a = 6.9741(3) Å, c = 17.190(2) Å, fractional positions and thermal factors for all atoms. The elastic constants (in GPa), obtained by fitting the spectroscopic data, are C ₁₁ = 181.9 ± 0.3, C ₃₃ = 66.8 ± 0.8, C ₄₄ = 42.8 ± 0.2, C ₁₂ = 48.2 ± 0.5, C ₁₃ = 27.1 ± 1.0, C ₁₄ = 5.4 ± 0.5, and C ₆₆ = ½(C ₁₁–C ₁₂) = 66.9 ± 0.3 GPa. The VRH averages of bulk and shear modulus are 63 and 49 GPa, respectively. The aggregate Poisson ratio is 0.19. The high value of the ratio C ₁₁/C ₃₃ = 2.7 and of the ratio C ₆₆/C ₄₄ = 1.6 are characteristic of an anisotropic structure with very weak interlayer interactions along the c-axis. The basal plane (001) is characterized by 0.1% longitudinal acoustic anisotropy and 0.9–1.1% shear acoustic anisotropy, which gives alunite a characteristic pseudo-hexagonal elastic behavior, and is related to the pseudo-hexagonal arrangement of the Al(O,OH)₆ octahedra in the basal layer. The elastic Debye temperature of alunite is 654 K. The large discrepancy between the elastic and heat capacity Debye temperature is also a consequence of the layered structure.     

High pressure phase equilibria in the system CaTiO3-CaSiO3: stability of perovskite solid solutions

Phase relations in the system CaTiO₃-CaSiO₃ were experimentally examined at 5.3–14.7 GPa and 1200–1600 °C with a 6–8 type multianvil apparatus. As pressure increases, stability field of perovskite solid solution extends from CaTiO₃ to CaSiO₃, and the perovskite becomes stable for the entire composition range above about 12.3 GPa. The stability field of Ca(Ti_1?X, Si_X)₂O₅ (0.78<x≦1) titanite solid solution +Ca₂SiO₄ larnite exists in the CaSiO₃-rich composition range at 9.3–12.3 GPa and 1200 °C. Perovskite solid solutions containing CaSiO₃ component of 0 to 66 mol% could be quenched to 1 atm. The composition-molar volume relationship of perovskite solid solution showed that molar volume of perovskite solid solution linearly reduces from the value of CaTiO₃ to that of CaSiO₃.     

Synthesis, properties and stability of end member boromuscovite, KAl2[BSi3O10](OH)2

End member boromuscovite, with nearly the ideal composition, was synthesized as a single phase from mixtures of its own composition, or with excess boron and water, at high pressures of between 15 and 30 kbar at 700 °C. The mica synthesized consists of a mixture of 2M₁ and 1M polytypes with the cell dimensions of 2M₁: a=5.071(4), b=8.786(4), c=19.830(89) Å, #=95.84(12)°, V=878.5(1.4) ų; and 1M: a=5.059(5), b=8.819(6), c=10.025(17) Å, #=101.39(57)°, V=438.4(1.3) Å. The IR spectrum shows characteristic differences relative to that of muscovite. DTA registers an endothermic peak due to dehydration breakdown above 680 °C. Seeded experiments indicate that boromuscovite is a high-pressure phase requiring minimum pressures of 3 to 10 kbar at temperatures that concomitantly increase from 300 to 750 °C. At lower pressures, the anhydrous solid assemblage K-feldspar + Al-borate (probably Al₄B₂O₉) coexists with a vapor rich in boric acid. The conversion of this assemblage to boromuscovite is connected with increases in the coordination number of B from [3] to [4], and of Al from [4] to [6]. Above 10 kbar, the boromuscovite stability field is limited along its high-temperature side by congruent (or incongruent?) melting of the mica, starting near 750 °C and 10 kbar and increasing to about 900 °C at 50 kbar, although, at such very high pressures a supercritical fluid may be present. Because, even in the presence of excess-boron fluid, the synthetic mica shows invariable X-ray properties, it is concluded that one B atom per formula unit represents the maximum, and - contrary to olenitic tourmalines - no further substitution of Si by B linked with addition of hydrogen takes place. In contrast to muscovite, KAl₂[AlSi₃O₁₀](OH)₂, end member boromuscovite is not stable under normal P-T conditions of the Continental Crust along a 30 °C/km geotherm, and especially not during the intrusion of acidic igneous rocks including their pegmatites, which may explain its scarcity in nature. However, it may form in the waning hydrothermal stages of deep-seated (>10.5 km) pegmatites and - providing sufficient boron is available - in HP/LT subduction zone environments, where it may carry boron to considerable depths.     

Experimental studies on the formation of inclusions in plagioclases from metatonalites,Hohe Tauern,Austria (lower temperature stability limit of the paragenesis anorthite plus potash feldspar)

New experimental data are presented at stability conditions of paragenesis in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O. These results are used to estimate the pressure temperature conditions under which minute inclusions, mostly consisting of zoisite/clinozoisite and muscovite, have crystallized in calcic plagioclases from metatonalites and metadiorites (Hohe Tauern, Austria). In the pressure region 1.5–8 kb the following reactions were observed: zoisite+muscovite+quartz=anorthite+potash feldspar+water (1) grossularite+muscovite+quartz=anorthite+potash feldspar+water (2) zoisite+quartz=anorthite+grossularite+water (3) natural plagioclase with its inclusions (zoisite/clinozoisite and muscovite) (4) =more basic plagioclase without inclusions.In order to determine the curves of reaction (1), (2) and (3), runs were made in hydrothermal bombs using synthetic phases crystallized from gels as starting materials. The reaction curves (1), (2) and (3) intersect at an invariant point at 7.25±0.5 kb and 685±20° C. In runs to define the reaction (4), it could be demonstrated that the inclusion minerals zoisite/ clinozoisite and muscovite became instable at slightly lower temperatures than those occurring in reaction (1). These facts illustrate that the reaction curve (1), found in the pure system, gives possible information about the pressure temperature conditions during the formation of the inclusions.     

High-pressure properties of diaspore,AlO(OH)

The structural compression mechanism and compressibility of diaspore, AlO(OH), were investigated by in situ single-crystal synchrotron X-ray diffraction at pressures up to 7 GPa using the diamond-anvil cell technique. Complementary density functional theory based model calculations at pressures up to 40 GPa revealed additional information on the pressure-dependence of the hydrogen-bond geometry and the vibrational properties of diaspore. A fit of a second-order Birch–Murnaghan equation of state to the p–V data resulted in the bulk modulus B ₀ = 150(3) GPa and B ₀ = 150.9(4) GPa for the experimental and theoretical data, respectively, while a fit of a third-order Birch–Murnaghan equation of state resulted in B ₀ = 143.7(9) GPa with its pressure derivative B′ = 4.4(6) for the theoretical data. The compression is anisotropic, with the a-axis being most compressible. The compression of the crystal structure proceeds mainly by bond shortening, and particularly by compression of the hydrogen bond, which crosses the channels of the crystal structure in the (001) plane, in a direction nearly parallel to the a-axis, and hence is responsible for the pronounced compression of this axis. While the hydrogen bond strength increases with pressure, a symmetrisation is not reached in the investigated pressure range up to 40 GPa and does not seem likely to occur in diaspore even at higher pressures. The stretching frequencies of the O–H bond decrease approximately linearly with increasing pressure, and therefore also with increasing O–H bond length and decreasing hydrogen bond length. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.     

Study on Al2O3 content and phase stability of aluminous-CaSiO3 perovskite at high pressure and temperature

 In order to clarify Al₂O₃ content and phase stability of aluminous CaSiO₃-perovskite, high-pressure and high-temperature transformations of Ca₃Al₂Si₃O₁₂ garnet (grossular) were studied using a MA8-type high-pressure apparatus combined with synchrotron radiation. Recovered samples were examined by analytical transmission electron microscopy. At pressures of 23–25 GPa and temperatures of 1000–1600 K, grossular garnet decomposed into a mixture of aluminum-bearing Ca-perovskite and corundum, although a metastable perovskite with grossular composition was formed when the heating duration was not long enough at 1000 K. On release of pressure, this aluminum-bearing CaSiO₃-perovskite transformed to the “LiNbO₃-type phase” and/or amorphous phase depending on its Al₂O₃ content. The structure of this LiNbO₃-type phase is very similar to that of LiNbO₃ but is not identical. CaSiO₃-perovskite with 8 to 25 mol% Al₂O₃ was quenched to alternating lamellae of amorphous layer and LiNbO₃-type phase. On the other hand, a quenched product from CaSiO₃-perovskite with less than 6 mol% consisted only of amorphous phase. Most of the inconsistencies amongst previous studies could be explained by the formation of perovskite with grossular composition, amorphous phase, and the LiNbO₃-type phase. Received: 11 April 2001 / Accepted: 5 July 2002     

High temperature phase equilibria in a solar-composition gas

Using recent additions to thermochemical data on minerals and information on their solid solution behavior, new equilibrium phase diagrams have been computed in a system of solar gas composition (Si, Al, Mg, Ca, Fe, Ni, Ti, Na, K, C, H, O, S, N) in the pressure and temperature ranges of 1 to 10^?6 bar and 1153 to 1773 K respectively. These calculations show that Fe-Ni alloy condenses before all silicates included here (except melilite) down to a pressure of 2 · 10^?4 bar below which plagioclase and clinopyroxene condense first. Orthopyroxene condenses next followed by ilmenite. Pressure-temperature variation of the chemical composition of melilite, clinopyroxene, orthopyroxene, metal alloy and plagioclase may be used for cosmothermometry and cosmobarometry for equilibrium assemblages.The major transition from the refractory oxides and melilite (the meteorite ‘inclusion assemblage’) to an assemblage of Fe-Ni alloy, olivine, plagioclase and pyroxenes (‘planet-forming’) takes place within a narrow interval of pressure and temperature. Small fluctuations of either pressure or temperature across this narrow region result in drastic changes in types and modes of minerals, which may explain the wide mineralogical varieties of meteorites.     

Solubility of rare earth elements in carbonatite magmas,indicated by the liquidus surface in CaCO3Ca(OH)2La(OH)3 at 1 kbar pressure

The system CaCO₃Ca(OH)₂(CCCH) represents a synthetic analog to a carbonatite magma. Addition of a light rare earth (RE) component La(OH)₃ (LH) gives a simple analog of a rare earth carbonatite. Liquidus relations for two joins were studied at 1 kbar pressure; CHLH and (CC₅₅CH₄₅)LH. CHLH is binary with a eutectic at CH₇₉LH₂₁ and 710°C. Thejoin CC₅₅ + CH₄₅)LH has a liquidus piercing point between CC and LH, at (CC₅₅CH₄₅)₆₀LH₄₀ and 700°C. Combining the new results with known results for CCCH allows construction of a liquidus diagram for part of the join CCCHLH. A ternary eutectic between the primary liquidus fields for CH, CC and LH occurs near 610°C with estimated composition CC= 33%,CH= 47%,LH= 20%. The solubility of La(OH)₃ in the synthetic carbonatite magma increases with increase of CO₂/H₂O from 20% at the eutectic to 40% at the piercing point on the join (CC₅₅CH₄₅)LH. The solubility of La in synthetic carbonatite is high compared with that of silicates. P₂O₅, and S. The results show that REE can become concentrated to high levels by fractionation of carbonatites, as long as they are not removed by high temperature crystallization of apatite and monazite.     

Interaction of B(OH)_3^0 and HCO_3^ - in Seawater: Formation of B(OH)_2 CO_3^ -

Boron is known to interact with a wide variety of protonated ligands(HL) creating complexes of the form B(OH)₂L^-.Investigation of the interaction of boric acid and bicarbonate in aqueoussolution can be interpreted in terms of the equilibrium $B(OH)_3^0 + HCO_3^ - \rightleftharpoons B(OH)_2 CO_3^ - + H_2 O$ The formation constant for this reaction at 25 °C and 0.7 molkg^-1 ionic strength is $K_{BC} = \left[ {B(OH)_2 CO_3^ - } \right]\left[ {B(OH)_3^0 } \right]^{ - 1} \left[ {HCO_3^ - } \right]^{ - 1} = 2.6 \pm 1.7$ where brackets represent the total concentration of each indicatedspecies. This formation constant indicates that theB(OH)₂ $CO_3^ - $ concentration inseawater at 25 °C is on the order of 2 μmol kg^-1. Dueto the presence of B(OH)₂ $CO_3^ - $ , theboric acid dissociation constant ( $K\prime _B $ ) in natural seawaterdiffers from $K\prime _B $ determined in the absence of bicarbonate byapproximately 0.5%. Similarly, the dissociation constants of carbonicacid and bicarbonate in natural seawater differ from dissociation constantsdetermined in the absence of boric acid by about 0.1%. Thesedifferences, although small, are systematic and exert observable influenceson equilibrium predictions relating CO₂ fugacity, pH, totalcarbon and alkalinity in seawater.     

Refinement of the crystal structure of papagoite,CaCuAlSi2O6(OH)3

Summary The crystal structure of papagoite, CaCuAlSi₂O₆(OH)₃, monoclinic,a = 2.926 (3),b = 11.496 (3),c = 4.696 (1) Å, = 100.81 (2)°, V = 685.4 (3) ų, space groupC 2/m,Z = 4, has been refined to anR index of 3.4% for 913 observed reflections measured with MoK X-radiation. The single unique Cu cation is surrounded by six anions in a pseudo-octahedral arrangement showing strong Jahn-Teller distortion. Edge-sharing rutile-like chains of pseudo-octahedrally coordinated Cu and Al extend in the Y direction, and are cross-linked into an octahedral sheet by Ca₂Ø₁₀ (O = unspecified ligand, O or OH) dimers. These sheets are linked by (Si₄O₁₂) rings to form a mixed tetrahedral-octahedral framework.

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Verfeinerung der Kristallstruktur von Papagoit, CaCuAlSi₂O₆(OH)₃

Zusammenfassung Die Kristallstruktur von Papagoit, CaCuAlSi₂O₆(OH)₃, monoklina = 12,926 (3),b = 11.496 (3),c = 4.696 (1) Å, = 100.81 (2)°,V = 685.4 (3) ų, RaumgruppeC2/m,Z = 4, wurde für 913 beobachtete, MoK-Röntgenstrahlung gemessene Reflexe aufR = 3,4% verfeinert. Das eine symmetrieunabhängige Kupfer-Kation ist pseudooktaedrisch von sechs Anionen mit einer starken Jahn-Teller-Verzerrung umgeben. Die pseudo-oktaedrisch koordinierten Cu- und Al-Atome werden über Kanten zu parallel zur y-Achse verlaufenden rutil-ähnlichen Ketten verbunden, die zusammen mit den Ca₂Ø₁₀-Gruppen (Ø = nicht spezifsierter Ligand, O bzw. OH) Oktaederschichten bilden. Diese Schichten werden durch (Si₄O₁₂)-Ringe zu einem aus Tetraedern und Oktaedern bestehenden Netzwerk verknüpft.

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With 4 Figures