Temperature-dependent magnetic susceptibility behaviour of spinelloid and spinel solid solutions in the systems Fe2SiO4–Fe3O4 and (Fe,Mg)2SiO4–Fe3O4

The magnetic behaviour and Curie temperatures (T _C ) of spinelloids and spinels in the Fe₃O₄–Fe₂SiO₄ and Fe₃O₄–(Mg,Fe)₂SiO₄ systems have been determined from magnetic susceptibility (k) measurements in the temperature range –192 to 700 °C. Spinelloid II is ferrimagnetic at room temperature and the k measurements display a characteristic asymmetric hump before reaching a T _C at 190 °C. Spinelloid V from the Mg-free system is paramagnetic at room temperature and hysteresis loops at various low temperatures indicate a ferri- to superparamagnetic transition before reaching the T _{C .} The T _C shows a non-linear variation with composition between –50 and –183 °C with decreasing magnetite component (X _Fe3O₄). The substitution of Mg in spinelloid V further decreases T _C . Spinelloid III is paramagnetic over nearly the total temperature range. Ferrimagnetic models for spinelloid II and spinelloid V are proposed. The T _C of Fe₃O₄–Fe₂SiO₄ spinel solid solutions gradually decrease with increasing Si content. Spinel is ferrimagnetic at least to a composition of X _Fe3O₄=0.20, constraining a ferrimagnetic to antiferromagnetic transition to occur at a composition of X _Fe3O₄<0.20. A contribution of the studied ferrimagnetic phases for crustal anomalies on the Earth can be excluded because they lose their magnetization at relatively low temperatures. However, their relevance for magnetic anomalies on other planets (Mars?), where these high-pressure Fe-rich minerals could survive their exhumation or were formed by impacts, has to be considered.     

Electric conductivity of Fe2SiO4–Fe3O4 spinel solid solutions

 The spinel solid solution was found to exist in the whole range between Fe₃O₄ and γ-Fe₂SiO₄ at over 10 GPa. The resistivity of Fe_{3− x} Si _x O₄ (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe³⁺ and Fe²⁺ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe₂SiO₄ component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe³⁺–Fe²⁺ electron hopping with increasing the total Si content. This is probably because a large number of Si⁴⁺ ions occupies the octahedral site and the adjacent Fe²⁺ keeping the local electric neutrality around Si⁴⁺ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe₃O₄) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si⁴⁺ substitution. Received: 15 March 2000 / Accepted: 4 September 2000     

Magnetic properties of the Fe2SiO4-Fe3O4 spinel solid solutions

 Magnetic measurement of Fe_{3− x} Si _x O₄ spinel solid solutions indicates that their Curie temperatures decrease gradually, but not linearly, from 851 to 12 K with increasing content of nonmagnetic ions Si⁴⁺. Magnetic hysteresis becomes more noticeable in solid solutions having a larger content of Fe₂SiO₄. Saturation magnetizations of Fe_{3− x} Si _x O₄ samples increase up to x=0.357 and they are easily saturated in the field of H=0.1 T. However, magnetization of the sample of x=0.794 does not approach saturation even at high field of H=7.0 T and has a large coercive force. The Si⁴⁺ disordered distribution is confirmed to be ^tetr[Fe³⁺ _{1− x + x t} Si⁴⁺ _{x (1− t )}] ^octa[Fe²⁺ _{1+ x} Fe³⁺ _{1− x − x t} Si⁴⁺ _{x t} ] O₄ by the spin moment, which is consistent with site occupancy obtained from X-ray crystal structure refinement. Their molecular magnetizations would be expressed as M _B={4(1+x)+10xt}μ_B as functions of composition parameter x and Si⁴⁺ ordering parameter t of the solid solution. The sample of x=0.794 is antiferromagnetic below the Néel temperature, mainly due to the octahedral cation interaction M _O–M _O, while both M _T–M _O and M _O–M _O interactions induce a ferrimagnetic property. Concerning magnetic spin configuration, in the case of x>0.42, the lowest dɛ level becomes a singlet, resulting in no orbital angular momentum. Received: 20 April 2000 / Accepted: 11 September 2000     

The crystal structure of sonoraite,Fe3+Te4+O3(OH)·H2O

Summary Sonoraite, FeTeO₃(OH)·H₂O, is monoclinic,P 2₁/c, witha=10.984(2),b=10.268(2),c=7.917(2) Å, =108.49(2)°. For 8 formula units per cell the calculated density is 4.179(2) g/cm³; the observed value is 3.95(1) g/cm³. The Supper-Pace automated diffractometer was used to collect 1884 independent reflections which were corrected for absorption. The structure was determined by an automated symbolic addition procedure. It was refined to a residualR of 6.2% using anisotropic temperature factors for the cations and isotropic temperature factors for the oxygen atoms. Chains of octahedra about Fe extend along [101]; edge-sharing pairs of these octahedra are joined by corner sharing. The Fe–Fe distances across the shared edges are 3.05 and 3.20 Å, short enough to suggest magnetic interactions. All but one H₂O are involved in the chains. The Te⁴⁺ ions have a pseudotetrahedral coordination, with three oxygen ions forming one face of the tetrahedron and the lone electron pair of Te occupying the fourth corner. The O–Te–O average bond angle is 95°. The Fe chains are tied together by Te–O bonds in all three dimensions.

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Die Kristallstruktur von Sonorait, Fe³⁺Te⁴⁺O₃(OH).H₂O

Zusammenfassung Sonorait, FeTeO₃(OH)·H₂O, ist monoklin, P 2₁/c, mit den folgenden Zelldimensionen:a=10,984(2),b=10,268(2),c=7,917(2) Å, =108,49(2)°. Mit 8 Formel-Einheiten errechnet man eine Dichte von 4,179(2) g/cm³; die gemessene Dichte beträgt 3,95(1) g/cm³. Das Supper-Pace automatische Diffraktometer wurde zur Sammlung von 1884 unabhängigen Reflexen benutzt, welche für Absorption korrigiert wurden. Die Struktur wurde mit Hilfe eines vollständig automatischen Programms für symbolische Addition bestimmt. Mit anisotropen Temperaturfaktoren für die Kationen und mit isotropen Temperaturfaktoren für die Sauerstoff-Atome wurde ein Residuum von 6,2% erreicht. Ketten von Eisen-Oktaedern erstrecken sich entlang [101]; Oktaeder-Paare mit gemeinsamen Kanten sind über Eckenverknüpfung verbunden. Die Fe–Fe-Abstände über die gemeinsamen Kanten betragen 3,05 und 3,20 Å, kurz genug, um zu magnetischer Wechselwirkung führen zu können. Nur ein H₂O-Molekül ist nicht Teil einer Kette. Die Te⁴⁺-Ionen befinden sich in pseudotetraedrischer Koordination; drei Sauerstoff-Ionen bilden eine Fläche des Tetraeders, die vierte Ecke wird durch das einsame Elektronenpaar von Te besetzt. Der Mittelwert des O–Te–O-Bindungswinkels beträgt 95° Die Fe-Ketten werden durch Te–O-Bindungen dreidimensional verbunden.

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With 3 Figures     

Magnetite activities across the MgAl2O4-Fe3O4 spinel join,with application to thermobarometric estimates of upper mantle oxygen fugacity

The activity of Fe₃O₄ component in MgAl₂O₄-Fe₃O₄ spinels has been measured at 900° and 1000° C and 1 atm total pressure using a zirconia oxygen electrolyte. As previously reported for the dilute Fe₃O₄ concentration region (Mattioli and Wood 1986a), magnetite activity at 1000° C is greater than at 900° C at constant Fe₃O₄ mole fraction, for compositions across the MgAl₂O₄-Fe₃O₄ join between 20 and 80 mol% Fe₃O₄ component. The 1-atm solvus crest lies between 900° and 1000° C and, at 900° C the limbs are at Fe₃O₄ mole fractions of 0.2 and 0.6 approximately.Application of the O'Neill and Navrotsky (1983, 1984) cation distribution model indicates that the unusual activity — composition behavior of Fe₃O₄ is caused by changes in the equilibrium state of disorder of mixed MgAl₂O₄-Fe₃O₄ spinels relative to the disordered Fe₃O₄ standard state. In addition, both stoichiometric volumes (Mattioli et al. 1987) and activities across the MgAl₂O₄-Fe₃O₄ join suggest that short range order is significant for this binary. Excess free energy terms must be added to ideal Fe₃O₄ activities formulated from equilibrium cation distributions in complex MgAl₂O₄-Fe₃O₄ spinels in order to increase Fe₃O₄ activities to values consistent with observation and to generate the apparent region of immiscibility at 900° C.We have applied our activity data to the estimation of upper mantle spinel-lherzolite oxygen fugacities. We calculated that minimum 's are about 2 log units below the synthetic QFM buffer at 15 kbar total pressure for Fe₃O₄ concentration of 2 mol%, in a Cr-free spinel phase. If a preliminary calibration of an additional 25 mol% Fe²⁺-substitution as FeCr₂O₄ or FeAl₂O₄ component is incorporated into Fe₃O₄ activity, then olivine-orthopyroxene-spinel assemblages of depleted-Type 1-spinel-lherzolite xenoliths indicate 's close to QFM at 15 kbar. This is in good agreement with previous thermobarometric estimates and in sharp contrast to 1 atm intrinsic measurements near IW.     

Single crystal growth of the modified spinel (β) and spinel (γ) phases of (Mg,Fe)2SiO4 and some geophysical implications

Single crystals of ferromagnesian orthosilicates with modified spinel (β) and spinel (γ) structure as large as 500 μm have been grown by solid state crystallization at high temperature and high pressure using an MA8-type apparatus driven in a 2,000-ton uniaxial press. This system is capable of generating pressures of 24.0 (±0.3) GPa at 2,400 (±50)°C for one hour in a sample assembly volume of 0.14 cm³. Crystals larger than 100 μm were observed to grow only at pressures within 5 percent of the phase boundary between the stability fields of the β and γ phases. Experimental determination of the phase boundaries between β or β+γ and γ phases for (Mg,Fe)₂SiO₄ has been extended to 22 GPa and 2,400°C. The effect of configurational entropy due to disordering is evaluated to be minimal on the basis of the cationic distribution in the synthesized samples; thus, we conclude that the phase boundary between β or β+γ and γ phases remains essentially linear to 2,400°C. In (Mg,Fe)₂SiO₄ solid solutions, the stability field of the γ phase shifts towards the lower pressures with increasing iron content at a rate of a 1 GPa for each 10 mole percent Fe. Assignment of the β→β+γ→γ transition to the seismic 550 km discontinuity is rejected by the present phase diagram results for (Mg_0.9Fe_0.1)₂SiO₄ and measurement of acoustic velocities for β and γ Mg₂SiO₄, but the discontinuity may be caused by a phase transition of pyroxene to a garnet-like structure.     

Elasticity of single-crystal MgAl2O4 spinel up to 1273 K by Brillouin spectroscopy

The adiabatic single-crystal elastic constants, C _ij , of stoichiometric magnesium aluminate spinel (MgAl₂O₄) have been measured up to 1273 K by highresolution Brillouin spectroscopy, using a 6-pass tandem Fabry-Pérot interferometer and an argon ion laser (514.5 nm). Two platelet samples were employed for probing the acoustic phonons along [100] and [110] directions by platelet and backscattering geometries. The measured temperature dependences of the elastic moduli show a distinct anomaly at 923 K in the shear modulus C _s = (C₁₁-C₁₂)/2 (along [110] direction) and the longitudinal modulus C₁₁ (along [100] direction). This anomaly is consistent with the order-disorder phase transition, resulting from the atomic exchange between Mg at the tetrahedral site and Al at the octahedral site, which has been well documented recently (Peterson et al. 1991; Millard et al. 1992) by neutron powder diffraction and ²⁷Al magic-angle spinning NMR. The values of the temperature derivatives of v _p , v _s , and K _s , in the temperature range 300–923 K, calculated by the Voigt-Reuss-Hill approximation are -0.40ms^?1 K^?1, -0.26ms^?1 K^?1, and -1.89 x 10^?2GPaK^?1.     

Vibrational spectroscopy of aluminate spinels at 1 atm and of MgAl2O4 to over 200 kbar

Single-crystal Raman and infrared reflectivity data including high pressure results to over 200 kbar on a natural, probably fully ordered MgAl₂O₄ spinel reveal that many of the reported frequencies from spectra of synthetic spinels are affected by disorder at the cation sites. The spectra are interpreted in terms of factor group analysis and show that the high energy modes are due to the octahedral internal modes, in contrast to the behavior of silicate spinels, but in agreement with previous data based on isotopic and chemical cation substitutions and with new Raman data on gahnite (～ ZnAl₂O₄) and new IR reflectivity data on both gahnite and hercynite (～Fe_0.58Mg_0.42Al₂O₄). Therefore, aluminate spinels are inappropriate as elastic or thermodynamic analogs for silicate spinels. Fluorescence sideband spectra yield complementary information on the vibrational modes and provide valuable information on the acoustic modes at high pressure. The transverse acoustic modes are nearly pressure independent, which is similar to the behavior of the shear modes previously measured by ultrasonic techniques. The pressure derivative of all acoustic modes become negative above 110 kbar, indicating a lattice instability, in agreement with previous predictions. This lattice instability lies at approximately the same pressure as the disproportionation of spinel to MgO and Al₂O₃ reported in high temperature, high pressure work.     

High-pressure crystal chemistry of phenakite (Be2SiO4) and bertrandite (Be4Si2O7(OH)2)

Compressibilities and high-pressure crystal structures have been determined by X-ray methods at several pressures for phenakite and bertrandite. Phenakite (hexagonal, space group R \(\bar 3\) ) has nearly isotropic compressibility with β=1.60±0.03×10^?4 kbar^?1 and β=1.45±0.07×10^?4 kbar^?1. The bulk modulus and its pressure derivative, based on a second-order Birch-Murnaghan equation of state, are 2.01±0.08 Mbar and 2±4, respectively. Bertrandite (orthorhombic, space group Cmc2₁) has anisotropic compression, with β _a =3.61±0.08, β _b =5.78±0.13 and β _c =3.19±0.01 (all ×10^?4 kbar^?1). The bulk modulus and its pressure derivative are calculated to be 0.70±0.03 Mbar and 5.3±1.5, respectively. Both minerals are composed of frameworks of beryllium and silicon tetrahedra, all of which have tetrahedral bulk moduli of approximately 2 Mbar. The significant differences in linear compressibilities of the two structures are a consequence of different degrees of T-O-T bending.     

Heat capacities of Fe2O3-bearing silicate liquids

Direct measurements of liquid heat capacity, using a Setaram HT1500 calorimeter in step-scanning mode, have been made in air on six compositions in the Na₂O-FeO-Fe₂O₃-SiO₂ system, two in the CaO-FeO-Fe₂O₃-SiO₂ system and four of natural composition (basanite, andesite, dacite, and peralkaline rhyolite). The fitted standard deviations on our heat capacity measurements range from 0.6 to 3.6%. Step-scanning calorimetry is particularly useful when applied to iron-bearing silicate liquids because: (1) measurements are made over a small temperature interval (10K) through which the ferric-ferrous ratio of the liquid remains essentially constant during a single measurement; (2) the sample is held in equilibrium with an atmosphere that can be controlled; (3) heat capacity is measured directly and not derived from the slope of enthalpy measurements with temperature. Liquid compositions in the sodic and calcic systems were chosen because they contain large concentrations of Fe₂O₃ (up to 19 mol%), and their equilibrium ferric-ferrous ratios were known at every temperature of measurement. These measurement have been combined with heat capacity (Cp) data in the literature on iron-free silicate liquids to fit Cp as a function of composition. A model assuming no excess heat capacity (linear combination of partial molar heat capacities of oxide components) reproduces the liquid data within error (±2.2% on average). The derived partial molar heat capacity of the Fe₂O₃ component is 240.9 ±7.9 J/g.f.w.-K, with a standard error reduced by more than a factor of two from that in earlier studies. The model equation, based primarily on simple, synthetic compositions, predicts the heat capacity of the four magmatic liquids within 1.8% on average.     

Experimental and theoretical study of (Fe2+, Mg)(Al,Fe3+)2O4 spinels: Activity-composition relationships,miscibility gaps,vacancy contents

The compositions of (Fe²⁺, Mg)(Al, Fe³⁺)₂O₄ spinels equilibrated with a l M (Fe²⁺, Mg)Cl₂ aqueous solution at 800°C, 4 kbars were determined. General considerations of reciprocal systems allow derivation of the exchange isotherm between a chloride aqueous solution and (Mg, Fe²⁺)Al₂O₄ spinels. They enable calculation of ΔG of the reaction: FeCl₂ + MgAl₂O₄ = MgCl₂ + FeAl₂O₄ΔG = 2.9 kcal at 800°C, 4 kbars and provide the activity-composition relationships for the binary join FeAl₂O₄-MgAl₂O₄, which shows a substantial positive deviation from ideality. Some tie-lines between coexisting aluminous and ferric spinels were also obtained in the (Fe²⁺, Mg)(Al, Fe³⁺)₂O₄ system.These experimental data are modeled by a Gibbs free energy formulation of the spinel solid solution (Lehmann and Roux, 1984), where the corrective function g₂, necessary to reproduce the deviations from ideality, is artificially split into two parts:

• 1.(1) A homogeneous second degree polynomial in the composition variables, containing only the terms specific to the reciprocal nature of the system, whose coefficients are deduced from ΔG of the exchange reaction: MgAl₂O₄ + FeFe₂O₄ = MgFe₂O₄ + FeAl₂O₄ΔG = 4.5 kcal at 800°C, 4 kbars
• 2.(2) A homogeneous second degree polynomial in the site occupancy fractions, to model the non-ideal behavior of the (Fe²⁺, Mg)Al₂O₄ and (Fe₂₊, Mg)Fe₂O₄ spinels and the miscibility gap along the Fe(Al, Fe³⁺)₂O₄ join.

A model of reciprocal spinel solution involving defect end-members is used to estimate the vacancy contents of the spinels in equilibrium with sesquioxides. In this case, the corrective function necessary to take into account the reciprocal nature of the system is no longer a second degree polynomial, but a rational fraction.     

钛掺杂磁铁矿吸附去除水中亚甲基蓝的研究

用一种新的合成方法在水相中合成了钛磁铁矿(Fe3-xTixO4),并用XRD和FTIR对已合成的Fe3-xTixO4进行了表征。结果表明:合成的Fe3-xTixO4为立方晶系尖晶石结构,样品中的钛离子都已经进入Fe3-xTixO4晶格中,且Fe3-xTixO4表面羟基量随着钛掺杂量的增加而增加。随后,以亚甲基蓝为模拟染料污染物,考察了Fe3-xTixO4的吸附性能。实验表明:钛掺杂能够显著促进Fe3-xTixO4对亚甲基蓝的吸附,吸附反应在0.5h内就能达到吸附平衡。     

Crystal structures and cation distributions in simple spinels from powder XRD structural refinements: MgCr2O4, ZnCr2O4, Fe3O4 and the temperature dependence of the cation distribution in ZnAl2O4

The crystal structure and cation distributions in the spinels MgCr₂O₄, ZnCr₂O₄, Fe₃O₄ and a suite of ZnAl₂O₄ samples annealed at 900 to 1400° C and then rapidly quenched, have been determined by powder X-ray diffraction, using several different X-ray procedures and both conventional structure-factor refinement and whole-pattern (or Rietveld) refinement methods. The chromite spinels are expected from crystal chemical considerations to have an almost completely normal cation distribution (inversion parameter, x, equal to zero). In agreement with this expectation, three samples of MgCr₂O₄ annealed at 900, 1100 and 1300° C, and ZnCr₂O₄ were all found to have x=0 within two estimated standard deviations (esd), suggesting that the accuracy with which cation distributions in spinels may be determined by powder XRD is close to the estimated precision. Slightly better results are obtained assuming neutral-atom scattering curves rather than half-ionized or fully ionized, but the differences are small (within the esd). The results from the Rietveld refinements are similarly in good agreement with those using the conventional structure factor refinement approach (agreement within the combined esd's), although in detail the Rietveld procedure sometimes produces small systematic differences in refined parameters. The suite of ZnAl₂O₄ spinels show a smooth increase in x from 0.01 at 900° C to 0.05 at 1300° C, and this behaviour is well described by the simple thermodynamic model for disordering in spinels with α_Zn-Al=89 kJ/mol, assuming β=?20 kJ/mol. The oxygen positional parameters for Fe₃O₄ are similar to those from published single crystal studies, indicating that the powder method also yields accurate interatomic distances in spinels.     

Back transformation and oxidation of (Mg,Fe)2SiO4 spinels at high temperatures

Based on the in situ and temperature-quench X-ray measurements, the back transformation in the (Mg, Fe)₂SiO₄-spinels has been characterized in terms of the transformation temperature (T _r ),mechanism and kinetics of the transformation, and of the end product(s), with specific emphasis on the effect of oxygen on this transformation. The in situ measurements were conducted to 900° C in vacuum (10^-4 to 10^-5 torr) and to 600° C in air using synchrotron radiation (SR) at Stanford Synchrotron Radiation Laboratory (SSRL). In the quench-type measurements, samples were heated in air to 1100° C, quenched and examined at ambient conditions using the conventional X-ray diffraction facilities. Important results are (1) in vacuum, all the spinels convert back into the olivine phase, with their T _r decreasing with increasing iron content; (2) the spinel olivine back transformation is a nucleation and growth type of transformation and can be described quantitatively using the Avrami equation; (3) in air, the (Mg, Fe)₂SiO₄-spinels with 0.2 mole fraction Fe or more are all oxidized, and the composition and phase of the end products depend upon the temperature and the starting composition; and (4) the oxidation of the iron-rich (Mg, Fe)₂SiO₄-spinels in air occurs at 350–400° C, which is significantly lower than its T _r ( 300° C) in vacuum.     

Reversible hydration in synthetic mixite, BiCu6(OH)6(AsO4)3·nH2O (n≤3): hydration kinetics and crystal chemistry

 The presence of zeolitic water, with a reversible hydration behaviour, was determined by structural and kinetic studies on synthetic mixite BiCu₆(OH)₆(AsO₄)₃·nH₂O (n≤3). X-ray diffraction and infrared-spectroscopic investigations were performed on single crystals. Isothermal thermogravimetric experiments were carried out to determine the reaction kinetics of the de- and rehydration processes. The single-crystal structure refinement of a fully hydrated crystal yielded five partially occupied Ow positions (Ow=oxygen atom of a H₂O molecule) within the tube-like channels of the hexagonal [BiCu₆(OH)₆(AsO₄)₃] framework. For the partially dehydrated form, with n≈1, at least two of these sites were found to be occupied significantly. In addition, the structural investigations allowed two different intra-framework hydrogen bonds to be distinguished that are independent of the extra-framework water distribution and are responsible for the stability of the self-supporting framework. The kinetic analysis of the rate data in the 298–343K temperature range shows that the dehydration behaviour obeys a diffusion-controlled reaction mechanism with an empirical activation energy of E _a ^dehyd=54±4 kJ mol^–1. A two-stage process controls rehydration of which the individual steps were attributed to an initial surface-controlled (E _a ^hyd-I=6±1 kJ mol^–1) and subsequent diffusion-controlled reaction mechanism (E _a ^hyd-II=12±1 kJ mol^–1). The estimated hydration enthalpy of 42±5 kJ mol^–1 supports the distribution model of molecular water within the channels based on a purely hydrogen-bonded network. Received June 26, 1996 / Revised, accepted November 11, 1996     

Synthesis and crystal structure of a triple chain silicate,Na2Mg4Si6O16(OH)2

In the system Na₂CO₃-MgO-SiO₂-H₂O a new sodium magnesium silicate was synthesized under hydrothermal conditions; 450–600 ° C and 300–1000 Kg/cm₂. The structure of the specimen was determined by X-ray powder methods, and its properties were studied by chemical, infrared and TG analyses. The specimen has a triple chain structure (space group, C2/c) with the ideal chemical composition, 4 (Na₂Mg₄Si₆O₁₆(OH)₂) and lattice parameters, a= 10.152(2), b=27.137(4), c=5.276(1) Å, and = 106.97(3) °.The essential feature of the structure is shown by the presence of SiO₄ tetrahedra linked to form chains which have three times the width of those in pyroxene. These triple chains have a periodicity, 5.27 Å, along their lengths, and are bonded to each other laterally by the brucite layer made up by eight Mg cations and sandwiched between two inward pointing bands of tetrahedra. These units are linked back to back by cations (Mg or Na) in the Na(2) site and by a large cation (Na) at the Na(1) site.     

Synthesis and crystal chemistry of kornerupine in the system MgO-Al2O3-SiO2-B2O3-H2O

Boron-bearing kornerupine was synthesized in the simplest possible model system at fluid pressures and temperatures both within and outside the stability field of boron-free kornerupine. Best conditions for synthesis of single-phase products are 7 kb and 830 °C. Microprobe and wet chemical analyses as well as X-ray studies indicate compositional variations of kornerupines regarding all five constituent components: Increasing B-contents (from 0.37 to 3.32 wt% B₂O₃) are correlated with decreasing OH^? values largely according to the Eq. B³⁺?3 H⁺; the ratio MgO∶Al₂O₃∶SiO₂ varies from 4∶3∶4 in the direction towards 1∶1∶1. Thus kornerupine exhibits an at least ternary range of solid solution in the system studied. Crystallochemically speaking it is significant that, although the Mg∶Al∶Si ratio of kornerupine may remain constant with increasing boron contents, the total number of cations per formula unit increases beyond the ideal number of 14.0 as given by Moore and Bennett (1968). Considering the presence of an additional structural site at (000) it is suggested that the introduction of boron initiates a sequence of substitutions such as $$B^{[4]} \to Si^{[4] } \to A1^{[4]} \to Mg^{[6]} \to \square$$ . The filling of this site, empty in boron-free kornerupine, by Mg is connected with a loss of hydrogen located near this site. Petrologically speaking an exchange reaction relation exists between kornerupine and its coexisting fluid according to the equation Boron-free kornerupine+B₂O₃=boron-kornerupine+H₂O. The molar fractions $$X_{B_2 O_3 } = B_2 O_3 /\left( {B_2 O_3 + H_2 O} \right)$$ of kornerupines exceed those of their coexisting fluids by about one order of magnitude. Fluids with relatively low X_{B 2 O 3} lead to the coexistence of kornerupine with boron-free minerals such as enstatite and sapphirine, fluids with relatively high X_{B 2 O 3} produce the boron-minerals grandidierite, sinhalite, and tourmaline (in the present system without Na!) in addition to kornerupine.     

The crystal structure of walpurgite, (UO2)Bi4O4(AsO4)2·2H2O

Summary The crystal structure of walpurgite has been determined from three-dimensional X-ray single crystal data and has been refined toR=0.041 for 1381 independent reflections using a crystal from Schneeberg, Sachsen. Walpurgite crystallizes triclinic, space group , witha=7.135 (2),b=10.426 (4),c=5.494 (1) Å, =101 47 (2), =110.82 (2), =88.20 (2)^o andV-374 A³. Cell content and chemical formula are (UO₂)Bi₄O₄(AsO₄)₂·2H₂O, which is one H₂O less than previously known. The structure consists of complex layers Bi₄O₄(AsO₄)₂·2H₂O extending parallel to (010). Each layer is built up from a network of bismuth and oxygen atoms, to both sides of which AsO₄ groups and water molecules are attached. (UO₂)O₄ octahedra link the layers parallel tob via the AsO₄ groups and thus simultaneously from UO₂(AsO₄)₂ chains parallel toc. The two independent Bi atoms are trivalent and form pronounced one-sided BiO polyhedra: 4–5 oxygens are at distances of 2.11–2.48 Å, 4 additional oxygens are at distances of 2.63–3.35 Å.

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Die Kristallstruktur des Walpurgins, (UO₂)Bi₄O₄(AsO₄)₂·2H₂O

Zusammenfassung Die Kristallstruktur des Walpurgins wurde anhand eines Kristalls von Schneeberg, Sachsen, mit dreidimensionalen Röntgen-Einkristalldaten bestimmt und für 1381 Reflexe aufR=0,041 verfeinert. Walpurgin kristallisiert triklin, Raumgruppe ,a=7,135 (2),b=10,426 (4),c=5,494 (1) Å, =101,47 (2), =110,82 (2), =88,20 (2)^o undV=374 ų. Zellinhalt und chemische Formel lauten (UO₂)Bi₄O₄(AsO₄)₂·2H₂O, das ist um ein H₂O-Molekül weniger als bislang bekannt. Die Struktur enthält kompliziert gebaute Bi₄O₄(AsO₄)₂·2H₂O-Schichten, die sich parallel (010) erstrecken. Jede Schicht besteht aus einem Netz von Wismut- und Sauerstoffatomen, an das zu beiden Seiten AsO₄-Gruppen und H₂O-Moleküle anknüpfen. (UO₂)O₄-Oktaeder verbinden die Schichten über die AsO₄-Gruppen parallel zub und bilden so gleichzeitig (UO₂)(AsO₄)₂-Ketten parallel zuc aus. Die zwei unabhängigen, dreiwertigen Wismutatome des Walpurgins sind von 4–5 Sauerstoffatomen in Abständen von 2,11–2,48Å einseitig koordiniert und darüber hinaus noch von vier weiteren Sauerstoffatomen in Abständen von 2,63–3,35 Å umgeben.

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With 4 Figures     

Crystal chemistry of selenates with mineral-like structures: V. Crystal structures of (H3O)2[(UO2)(SeO4)2(H2O)](H2O)2 and (H3O)2[(UO2)(SeO4)2(H2O)](H2O), new compounds with rhomboclase and goldichite topology

The crystal structures of two new compounds (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O)₂ (1, orthorhombic, Pnma, a = 14.0328(18), b = 11.6412(13), c = 8.2146(13) Å, V = 134.9(3) ų) and (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O) (2, monoclinic, P2₁/c, a = 7.8670(12), b = 7.5357(7), c = 21.386(3) Å, β = 101.484(12)°, V = 1242.5(3) ų) have been solved by direct methods and refined to R ₁ = 0.076 and 0.080, respectively. The structures of both compounds contain sheet complexes [(UO₂)(SeO₄)₂]^2? formed by cornershared [(UO₂)O₄(H₂O)] bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the (100) plane in structure 1 and to (?102) in structure 2. The [(UO₂)(SeO₄)₂(H₂O)]^2? layers are linked by hydrogen bonds via interlayer groups H₂O and H₃O⁺. The sheet topologies in structures 1 and 2 are different and correspond to the topologies of octahedral and tetrahedral complexes in rhomboclase (H₂O₂)⁺[Fe(SO₄)₂(H₂O)₂] and goldichite K[Fe(SO₄)₂(H₂O)₂](H₂O)₂, respectively.