Magnesiochloritoid: Compressibility and high pressure structure refinement

The response of magnesiochloritoid to pressure has been studied by single crystal X-ray diffraction in a diamond anvil cell, using crystals with composition Mg_1.3Fe_0.7Al₄Si₂O₁₀(OH)₄. The unit cell parameters decrease from a = 9.434 (3), b = 5.452 (2), c = 18.136 (5) Å, β = 101.42° (2) (1 bar pressure) to a = 9.370 (7), b = 5.419 (5), c = 17.88 (1) Å, β = 101.5° (1) (42 kbar pressure), following a slightly anisotropic compression pattern (linear compressibilities parallel to unit cell edges: β _a = 1.85, β _b = 1.74, β_c = 3.05 × 10^?4 kbar^?1) with a bulk modulus of 1480 kbar. Perpendicular to c, the most compressible direction, the crystal structure (space group C2/c) consists of two kinds of alternating octahedral layers connected via isolated SiO₄ tetrahedra. With increasing pressure the slightly wavy layer [Mg_1.3Fe_0.7AlO₂(OH)₄] tends to flatten. Furthermore, the octahedra in this layer, with all cations underbonded, are more compressible than the octahedra in the (A1₃O₈) layer with slightly overbonded aluminum. Comparison between high-pressure and high-temperature data yields the following equations: $$\begin{gathered} a_{P,T} = 9.434{\text{ }}{\AA} - 174 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 9 \cdot 10^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ b_{P,T} = 5.452{\text{ }}{\AA} - 95 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 5 \cdot 65 \cdot 10^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ c_{P,T} = 18.136{\text{ }}{\AA} - 549 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 16 \cdot 2^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ \end{gathered} $$ with P in kbar and T in °C. These equations indicate that the unit cell and bond geometry of magnesiochloritoid at formation conditions do not differ greatly from those at the outcrop conditions, e.g. the calculated unitcell volume is 917.3 ų at P = 16 kbar and T=500 °C, whereas the observed volume at room conditions is 914.4 ų. In addition, they show that the specific gravity increases from formation at depth to outcrop at surface conditions.     

Raman spectra from the Al2SiO5 polymorphs at high pressures and room temperature

Raman spectra of the three Al₂SiO₅ polymorphs; andalusite, sillimanite and kyanite were recorded as a function of pressure at room temperature. All the Raman active bands which could be observed from the high-pressure cell showed a linear pressure dependence for each of the three Al₂SiO₅ polymorphs and no phase changes were observed over the pressure ranges used in this study. In andalusite and to a lesser extent in sillimanite, vibrations which could be correlated with internal motions of the SiO₄ tetrahedra were generally well separated from the lattice modes and showed a greater pressure dependence than that observed for other modes. The distinct pressure dependence of the internal SiO₄ modes is less evident in kyanite, probably due to the lack of continuous tetrahedral chains and the fact that the rigid SiO₄ tetrahedra now form an integral part of the structural network. At ambient pressure, kyanite also exhibits two fluorescence bands at 705 and 706.2 nm which are due to small amounts of Cr³⁺ in the kyanite crystals. These fluorescence bands showed a non-linear frequency shift as pressure was increased.     

高压下天然菱铁矿的压缩性和电子结构研究

采用同步辐射光源和金刚石对顶砧(DAC)技术,对天然菱铁矿的压缩性和电子结构进行了原位X射线衍射(XRD)和X射线吸收近边结构谱(XANES)测试研究。在室温下随着压力逐渐升高至50.2 GPa,菱铁矿保持方解石型结构不变,但是逐渐向Na Cl型结构转变;刚性[CO3]2-基团平行于ab-平面定向排列使c轴的压缩性大于a轴。菱铁矿在44.6~47.1 GPa之间发生电子由高自旋态(HS)向低自旋态(LS)的转变,表现为体积塌陷8%。HS菱铁矿的等温状态方程参数为K0=112(5)GPa和K'0=4.6(3)。首次采用XANES技术对菱铁矿中Fe2+的电子结构进行了研究,结果表明:随着压力升高至37.3 GPa,Fe2+的配位和局域对称并未发生明显变化;此后电子结构开始转变,Fe2+的3d轨道分裂能降低,电子跃迁概率增大,呈现LS特性。     

Electronic structure and electric field gradient calculations of Al2SiO5 polymorphs

 The electronic structure of the three polymorphs of Al₂SiO₅, andalusite, sillimanite, and kyanite, is studied by linearized-augmented-plane-wave (LAPW) calculations using the WIEN code. Total energy calculations verify, in agreement with recent pseudopotential calculations, that andalusite is the most stable phase, followed by sillimanite and kyanite.We determine the electronic charge density distribution and find strong polarizations on all oxygen ions. We identify different polarizations due to Al or Si neighbors which depend on their respective distances to the oxygen atom. The chemical bonding is not purely ionic in nature but has important covalent contributions. Electric field gradients (EFGs) at all sites are calculated and agree well (within 10%) with available experimental data on Al. We identify the origin of the EFGs and demonstrate its relation to the nearest-neighbor coordination and the resulting anisotropy of the electronic charge distribution. Received: 22 March 2000 / Accepted: 3 August 2000     

The relationship of elasticity and crystal structure in andalusite and sillimanite

The nine elastic constants of andalusite and sillimanite have been determined, using the technique of Brillouin scattering. They are, in megabars, for andalusite: c ₁₁=2.334, c ₂₂=2.890, c ₃₃=3.801, c ₄₄=0.995, c ₅₅=0.878, c ₆₆=1.123, c ₂₃=0.977, c ₁₃=1.162, c ₁₂=0.814; for sillimanite: c ₁₁=2.873, c ₂₂=2.319, c ₃₃=3.884, c ₄₄=1.224, c ₅₅=0.807, c ₆₆=0.893, c ₂₃=1.586, c ₁₃=0.834, c ₁₂=0.947. Both structures are characterized by chains of edge-linked coordination octahedra extending parallel to the crystallographic c direction, cross-linked by polyhedra of lower coordination. In each structure the stiffness measured parallel to c is greater than that measured normal to c. The shear moduli can be directly correlated with the relative rigidity of the cross-linking structures.     

Synthesis and some properties of iron- and vanadium-bearing kyanites, (Al,Fe3+)2SiO5and (Al,V3+)2SiO5

Iron- and vanadium-bearing kyanites have been synthesized at 900 and 1100° C/20 kb in a piston-cylinder apparatus using Mn₂O₃/Mn₃O₄- and MnO/Mn-mixtures, respectively, as oxygen buffers. Solid solubility on the pseudobinary section Al₂SiO₅-Fe₂SiO₅(-V₂SiO₅) of the system Al₂O₃-Fe₂O₃(V₂O₃)-SiO₂ extends up to 6.5 mole% (14mole %) of the theoretical end member FeSiO₅(V₂SiO₅) at 900°C/20 kb. For bulk compositions with higher Fe₂SiO₅ (V₂SiO₅) contents the corundum type phases M₂O₃(M = Fe³⁺, V³⁺) are found to coexist with the Fe³⁺(V³⁺)-saturated kyanite solid solution plus quartz. The extent of solid solubility on the join Al₂SiO₅-Fe₂SiO₅ at 1 100°C was not found to be significantly higher than at 900° C. Microprobe analyses of iron bearing kyanites gave no significant indication of ternary solid solubility in these mixed crystals. Lattice constants a ₀, b ₀, c ₀, and V₀ of the kyanite solid solutions increase with increasing Fe₂SiO₅- and V₂SiO₅-contents proportionally to the ionic radii of Fe³⁺ and V³⁺, respectively, the triclinic angles ,, remain constant. Iron kyanites are light yellowish-green, vanadium kyanites are light green. Iron kyanites, (Al_1.87 Fe _0.13 ³⁺ )SiO₅, were obtained as crystals up to 700 m in length.     

Compressibility of P2O5-Al2O3-Na2SiO3 melts

The effect of composition and temperature on the relaxed adiabatic bulk modulus of melts in the P₂O₅-Al₂O ₃-Na₂SiO₃ system have been investigated in the temperature range of 1140 to 1450 °C using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz. The density of these melts was determined using Pt-double-bob Archimedean densitometry techiques. P₂O₅ is known to dramatically affect the structure and the chemical and physical properties of granitic and pegmatitic melts as a function of the peralkalinity of the melt. The physical results of the structural changes occurring in Na₂O-Al₂O₃-SiO₂ melt upon the addition of P₂O₅ are observed by variations in the properties such as density and compressibility. For the present peralkaline melts, the bulk modulus and density decrease with addition of 15 mol% P₂O₅, and increase with the addition of 15 mol% Al₂O₃. The addition of P₂O₅ to the present melts results in a larger increase in melt compressibility than that observed with increasing polymerization between Na₂SiO₃ and Na₂Si₂O₅ melts. This would suggest that not only is the polymerization of the melt increasing with the addition of P₂O₅ (Mysen et al. 1981; Nelson and Tallant 1984; Gan and Hess 1992), but that the tetrahedrally co-ordinated phosphorus complexes are influencing the bond lengths and energies within the melt structure; resulting in the structure becoming more compressible than expected, although incompressible (Vaughan and Weidner 1987) tetrahedral P₂O₅ polyhedra (Mysen et al. 1981; Gan and Hess 1992; Toplis et al. 1994) are being added to the melt structure.     

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.     

Thermodynamics and behavior of γ-Mg2SiO4 at high pressure: Implications for Mg2SiO4 phase equilibrium

Raman spectra of γ-Mg₂SiO₄ taken to 200 kbar were used to calculate entropy and heat capacity at various P-T conditions. These new thermodynamic data on γ-MgSiO₄, similar data on MgSiO₃ perovskite (pv), previous data on β-MgSiO₄ and MgO (mw), and previous volumetric data of all phases were used to calculate the phase boundaries in the Mg₂SiO₄ phase diagram. Our resulting slope for the β→γ transition (50±4 bar K^-1) is in excellent agreement with recent multi-anvil studies. The slopes for the β→pv+MgO and γ→pv+MgO are-7±3 and -25±4 bar K^-1, respectively, and are consistent with our CO₂ laser heated diamond anvil studies. These slopes result in a β-γ-MgO+pv triple point at approximately 229 kbar and 2260 K for the iron free system.     

Solid solubility of Al2O3 in enstatite at high temperatures and 1–5 kb water pressure

Solid solubility of Al₂O₃ in orthorhombic enstatite by the substitution AlAl=MgSi is, in the range studied, mainly a function of temperature and not strongly pressure-dependent. Even at 1 kb up to 9 wt.-% Al₂O₃ can be substituted at 1200° C. The thermal stability of the orthorhombic pyroxene phase is strongly increased by the incorporation of Al.In crustal rocks the alumina content of orthopyroxene might be used as a geothermometer but not, as sometimes suggested, as a barometer.     

In situ observation of a phase transition in Fe2SiO4 at high pressure and high temperature

We used an in situ measurement method to investigate the phase transition of Fe₂SiO₄ polymorphs under high pressures and temperatures. A multi-anvil high-pressure apparatus combined with synchrotron X-ray radiation was used. The stability of each polymorph was identified by observing the X-ray diffraction data from the sample. In most experiments, the diffraction patterns were collected 10–30 min after reaching the desired pressure and temperature conditions. The transition boundary between the olivine and spinel phase at T = 1,000–1,500 K and P = 2–8 GPa was determined to occur at P (GPa) = 0.5 + 0.0034 × T (K). The transition pressure determined in this study was in general agreement with that observed in previous high-pressure experiments. However, the slope of the transition, dP/dT, determined in our study was significantly higher than that estimated by the previous study combined with the in situ X-ray method.     

The crystal structure of Ca5(PO4)2SiO4 (Silico-Carnotite)

Summary The crystal structure of Ca₅(PO₄)₂SiO₄ (silico-carnotite) has been determined from 3358 x-ray diffraction data collected by a counter method and has been refined toR _w =0.038,R=0.045, in space group Pnma. The unit cell parameters area=6.737 (1) Å,b=15.508 (2) Å andc=10.132 (1) Å at 24°C;Z=4. The observed density is 3.06 and the calculated density is 3.03 g · cm^–3. The crystal contains about 2.5% V₂O₅ as an impurity. The bond lengths within the tetrahedral anions suggest that substitution or disorder of PO₄ ^3–, SiO₄ ^4– and possibly VO₄ ^3– occurs among the anion sites. The structure has some relationship to that of Ca₅(PO₄)₃OH, the predominant inorganic phase in the human body, but suggests that the Ca₅(PO₄)₃OH type structure may not be stable without some of the OH positions being filled. Ca₅(PO₄)₂SiO₄ is more closely related to K₃Na(SO₄)₂ (glaserite) if it is considered that there are systematic cation vacancies in Ca₅(PO₄)₂SiO₄.This type of structure is consistent with the view that cation vacancies in the glaserite-type structure account for solid solutions between Ca₂SiO₄ and Ca₃(PO₄)₂ and between Ca₃(PO₄)₂ and CaNaPO₄.

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Die Kristallstruktur vonCa ₅(PO ₄)₂ SiO ₄ (Silicocarnotit)

Zusammenfassung Die Kristallstruktur von Ca₅(PO₄)₂SiO₄ (Silicocarnotit) wurde aus 3358 Röntgendiffraktometer-Daten bestimmt und in Raumgruppe Pnma aufR _w =0,038,R=0,045 verfeinert. Die Gitterkonstanten (bei 24° C) sind:a=6,737 (1) Å,b=15,508 (2) Å undc=10,132 (1) Å,Z=4; D_obs.=3,06 g · cm^–3, D_exp.=3,03 g · cm^–3. Der Kristall enthält etwa 2,5% V₂O₅ als Verunreinigung. Die Bindungslängen in den tetraedrischen Anionen legen nahe, daß unter den Anionenplätzen gegenseitige Vertretung oder Unordnung von PO₄ ^3–, SiO₄ ^4– und möglicherweise VO₄ ^3– auftritt. Die Struktur zeigt einige Verwandtschaft zu der von Ca₅(PO₄)₃OH, der wichtigsten anorganischen Substanz im menschlichen Körper, weist aber darauf hin, daß eine Struktur vom Ca₅(PO₄)₃OH-Typ ohne Besetzung eines Teiles der OH-Position nicht stabil ist. Ca₅(PO₄)₂SiO₄ zeigt engere Beziehungen zu K₃Na(SO₄)₂ (Glaserit), wenn man berücksichtigt, daß in Ca₅(PO₄)₃SiO₄ systematische Kationen-Leerstellen sind. Dieser Strukturtyp ist mit derAuffassung in Übereinstimmung, daß Kationenleerstellen für die festen Lösungen zwischen Ca₂SiO₄ und Ca₃(PO₄)₂ und zwischen Ca₃(PO₄)₂ und CaNaPO₄ verantwortlich sind.

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With 9 Figures     

Dislocation strain energy in the Al2SiO5 polymorphs

Molar elastic strain energy arising from dislocations in andalusite and sillimanite were calculated using equations derived from a non-core, linear elasticity model. For perfect (unit) c screw dislocations in these polymorphs, minimum dislocation densities of about 10¹⁰/cm² are necessary to significantly perturb the andalusite=sillimanite equilibrium boundary in P-T space. Compared to unit c dislocations, smaller energy perturbations arise from dissociated c screw dislocations, which are commonly observed in kyanite and sillimanite. A low computed value of stacking fault energy (～30 ergs/cm²) in these polymorphs is compatible with the large separations of dissociated dislocations in these phases. Dislocation densities in naturally occurring Al₂SiO₅ polymorphs are typically <10⁸/cm². Assuming that these densities are representative of those existing during metamorphism, as is supported by the lack of microtextures indicative of strong recovery, it is concluded that molar strain energies corresponding to observed dislocation densities (<10⁸/cm²) result in insignificant perturbation of P-T phase equilibrium boundaries of the Al₂SiO₅ polymorphs.     

ELF isosurface maps for the Al2SiO5 polymorphs

This study examines the electron localization function (ELF) isosurfaces of the Al₂SiO₅ polymorphs kyanite, sillimanite, and andalusite to see how differences in coordination and geometry of the cations and anions affect the ELF isosurfaces. Examination of the ELF isosurfaces indicates that their shapes are dependent on the coordination and geometry of the oxygen atoms and are not sensitive to coordination of the surrounding cations. Of the 18 crystallographically distinct oxygen atoms in the Al₂SiO₅ polymorphs, 13 are bonded to two aluminum atoms and one silicon atom (Al₂–O–Si) and are associated with two different ELF isosurface shapes. The shape of the ELF isosurface is dependent on the distance at which the oxygen atom lies from a plane defined by the three surrounding cations: at a distance greater than 0.2 Å the ELF can be defined as horseshoe-shaped and at a distance less then 0.2 Å it can be described as concave hemispherical. This feature is also seen in the ELF isosurfaces for the oxygens bonded to three aluminum atoms (Al₃–O) where the isosurfaces can be defined as trigonally toroidal and uniaxially trigonally toroidal. The changes in the ELF isosurfaces for the three coordinated oxygens are also indicative of changes in hybridization. The ELF isosurface for the two-fold coordinated oxygen (Al–O–Si) has a large mushroom-shaped isosurface along the Al–O bond and a concave hemispherical isosurface along the Si–O. The four-fold coordinated oxygen (Al₄–O) contains two concave hemispherical isosurfaces along the shorter Al–O bonds and a banana-shaped isosurface, which encompasses the longer Al–O bonds. In addition, this study shows the homeomorphic relationship between the ELF isosurfaces and electron density difference maps with respect to number and arrangement of domains.     

Compressibility and structure behaviour of maruyamaite (K-tourmaline) from the Kokchetav massif at high pressure up to 20 GPa

Mineralogy and Petrology - The structural behaviour of maruyamaite (K-dominant tourmaline) X(K0.54Na0.28Ca0.19)Y(Mg1.3Al1.17Fe0.39Ti0.14)Z(Al5Mg)[Si5.95Al0.05O18](BO3)3V,W[O1.69(OH)2.31] from the...     

Decomposition of kyanite and solubility of Al2O3 in stishovite at high pressure and high temperature conditions

In order to constrain the high-pressure behavior of kyanite, multi-anvil experiments have been carried out from 15 to 25 GPa, and 1,350 to 2,500°C. Both forward and reversal approaches to phase equilibria were adopted in these experiments. We find that kyanite breaks down to stishovite + corundum at pressures above ∼15 GPa, and stishovite + corundum should be the stable phase assemblage at the pressure–temperature conditions of the transition zone and the uppermost part of the lower mantle of the Earth, in agreement with previous multi-anvil experimental studies and ab initio calculation results, but in disagreement with some of the diamond-anvil cell experimental studies in the literature. The Al₂O₃ solubility in nominally dry stishovite has been tightly bracketed by forward and reversal experiments; it is slightly but consistently reduced by pressure increase. Its response to temperature increase, however, is more complicated: increases at low temperatures, maximizes at around 2,000°C, and perhaps decreases at higher temperatures. Consequently, the Al₂O₃ solubility in dry stishovite at conditions of high temperature–high pressure is very limited.     

The crystal and melt structure of spinel and alumina at high temperature: An in-situ XANES study at the Al and Mg K-edge

We present structural information obtained on spinel and alumina at high temperature (298-2400 K) using in-situ XANES at the Mg and Al K-edges. For spinel, ^[4](Al_x,Mg_1−x)^[6](Al_2−x,Mg_x)O_4, with increasing temperature, a substitution of Mg by Al and Al by Mg in their respective sites is observed. This substitution corresponds to an inversion of the Mg and Al sites. There is a significant change in the Al K-edge spectra between crystal and liquid, which can be attributed to a change of the ^[6]Al normally observed in corundum at room temperature, to a mixture of ^[6]Al-^[4]Al in the liquid state. This conclusion is in good agreement with previous ²⁷Al NMR experiments. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.     

In situ determination of crystal structure for high pressure phase of ZrO2 using a diamond anvil and single crystal X-ray diffraction method

Combining a miniature diamond-anvil pressure cell with a single crystal four-circle diffractometer, the crystal structure of a synthetic ZrO₂ has been studied in situ up to 51 kbar at room temperature. The space group of the unquenchable orthorhombic high pressure phase is Pbcm. The directions of the b and c axes are preserved through the transition and the transformation is displacive. The coordination configurations of the Zr atoms and oxygen atoms are the same in the high pressure and low pressure phases. The orthorhombic high pressure phase has a higher entropy than that of low pressure monoclinic phase.     

Synthetic Mn3+-kyanite and viridine, (Al2-xMn x 3+ ) SiO5, in the system Al2O3-MnO-MnO2-SiO2

Experiments on the join Al₂SiO₅-“Mn₂SiO₅” of the system Al₂O₃-SiO₂-MnO-MnO₂ in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn₂O₃, and high purity SiO₂ as starting materials and using /_O2-buffer techniques to preserve the Mn³⁺ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al_1.88Mn _0.12 ³⁺ )SiO₅ and, thus, equals approximately that on the join Al₂SiO₅-“Fe₂SiO₅” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn³⁺ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a _o, b _o, c _o, and V _o to increase by 0.015, 0.009, 0.014 Å, and 1.6 ų, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn³⁺-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusite_ss (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al_1.86Mn _0.14 ³⁺ )SiO₅-(Al_1.56Mn _0,44 ³⁺ )SiO₅. Thus, Al→Mn³⁺ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn³⁺ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a _o, b _o, c _o, and V _o to increase by 0.118, 0.029, 0.047 Å and 9.4 ų, resp. At “Mn₂SiO₅”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn₂SiO₅”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn²⁺Mn³⁺[O₈/Si0₄]), pyrolusite and SiO₂ were found to coexist with the Mn³⁺-saturated ky _ss or and _ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn³⁺). Pure synthetic braunites had the lattice constants a _o 9.425, c _o, 18.700 Å, V _o 1661.1 ų (ideal compn.) and a _o 9.374, c _o 18.593 ų, V _o 1633.6 ų (1 Al for 1 Mn³⁺). Stable coexistence of the Mn²⁺-bearing phase braunite with the Mn⁴⁺-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO₂-SiO₂.