Thermal expansion,heat capacity,and entropy of MgO at mantle pressures

The pressure dependence of the Raman spectrum of forsterite was measured over its entire frequency range to over 200 kbar. The shifts of the Raman modes were used to calculate the pressure dependence of the heat capacity, C _v, and entropy, S, by using statistical thermodynamics of the lattice vibrations. Using the pressure dependence of C _v and other previously measured thermodynamic parameters, the thermal expansion coefficient, , at room temperature was calculated from = K _S (T/P) _S C _V/TVK _T, which yields a constant value of ( ln / ln V)_T= 6.1(5) for forsterite to 10% compression. This value is in agreement with ( ln / ln V)_T for a large variety of materials.At 91 kbar, the compression mechanism of the forsterite lattice abruptly changes causing a strong decrease of the pressure derivative of 6 Raman modes accompanied by large reductions in the intensities of all of the modes. This observation is in agreement with single crystal x-ray diffraction studies to 150 kbar and is interpreted as a second order phase transition.     

Hydrostatic compression of γ-(Mg0.6, Fe0.4)2SiO4 to 50.0 GPa

The bulk modulus, K ₀, and its pressure derivative K₀, of -(Mg_0.6, Fe_0.4)₂SiO₄ have been accurately determined to 50.0 GPa under hydrostatic conditions at room temperature in a diamond cell using synchrotron radiation. Our results agree with Brillouin and ultrasonic measurements on -Mg₂SiO₄ at low pressure, indicating normal elastic behaviour in the metastable pressure range of this high pressure mineral. Our values of K ₀ and k₀ are 183.0 GPa and 5.4, respectively.     

Compression of α-MnS (alabandite) and a new high-pressure phase

The compressibility of -Mns (alabandite) was determined by x-ray analysis using a Mao-Bell type diamond anvil cell. The zero pressure bulk modulus (K₀) is 74±2 GPa with the pressure derivative of the bulk modulus (K_o) fixed at four. Allowing (K_o) to vary yielded a statistically better fit with K₀ = 88±6 GPa and k₀ = 2.2±0.6. Our data combined with the data of McCammon (1991) gave K_o = 73±1 GPa with k_o fixed at four. A fit with k_o allowed to vary yielded k_o = 75±2 GPa and k_o = 3.7±0.4. Alabandite transformed from the B1 structure (NaCl-type) to an unknown high-pressure phase at 26 GPa. The high-pressure phase has lower than hexagonal symmetry and it is stable to at least 46±4 GPa.Also affiliated with the James Franck Institute, University of Chicago     

Al-Si ordering in Sr-feldspar SrAl2Si2O8: IR,TEM and single-crystal XRD evidences

Al-Si ordering in Sr-feldspar has been followed by isothermal annealing, starting from a disordered metastable configuration. Ordering could not be followed by changes in the spontaneous strain as cell parameters did not show significant changes with thermal treatment from 0.016 h to 452 h at T=1350° C, while, on the contrary, significant changes in IR spectra are observed. A single crystal obtained from melt (Q _od 0) has been progressively heated up to 678 h at T=1350° C and the relevant structural refinements enabled to monitor changes in degree of Al-Si order up to Q_od = 0.86. In isothermal treatment for Sr-feldspar it is observed a significantly lower Q _od than in anorthite after the same annealing time. TEM observation has shown in Sr-feldspar, also for shortest annealing, b type reflections, while in anorthite, in the same conditions, e type reflections have been observed (Carpenter 1991a). In the first stages of ordering b APDs sized 100 Å (at T=1350° C, 0.33 h) have been observed in Sr-feldspar; APD coarsening occurs with an activation energy of 120±7 kcal mol^-1, not significantly different from anorthite. The ordering process seems to be a slower process in Sr-feldspar than in anorthite, even though data from longer annealing suggest that the Q _od close to the equilibrium is the same in Sr and Ca-feldspar (Q _od = 0.86 at T=1350° C).     

Der Strukturtyp von Emmonsit, {Fe2[TeO3]3·H2O}·xH2O (x=0−1)

Zusammenfassung Emmonsit kristallisiert triklin, RaumgruppeP , Gitterkonstanten:a ₀=7,90 Å,b ₀=8,00 Å,c ₀=7,62 Å, =96^o44, =95^o 0, =84^o 28,Z=2. Der Strukturtyp wurde aus 3-dimensionalen photographischen Röntgendaten ermittelt. Die Eisenatome werden je von 6 Sauerstoffen verzerrt oktaedrisch koordiniert. Jedes Telluratom wird von 3 Sauerstoffen in einem Abstand <2,0 Å umgeben. Ein vierter Sauerstoff hat bezüglich dieser drei einen um etwa 25–35% größeren Abstand, so daß jedes Telluratom im weiteren Sinne eine (3+1)-Koordination aufweist.

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The structure type of emmonsite, {Fe₂[TeO₃]₃·H₂O}·xxH₂O (x=0–1)

Summary Emmonsite is triclinic with space groupP , and lattice constantsa ₀=7.90 Å,b ₀=8.00 Å,c ₀=7.62 Å, =96^o 44, =95^o 0, =84⁰ 28,Z=2. The structure type is derived from 3-dimensional photographic X-ray data. The iron atoms are coordinated by six oxygens in the form of a distorted octahedron. Each tellurium atom is coordinated to 3 oxygens at a distance <2.0 Å. Compared with these 3 Te–O distance the distance of a fourth oxygen is only 25 to 35% greater; therefore each tellurium atom has a (3+1)-coordination of oxygens.

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Electron paramagnetic resonance of Sc3+-stabilized CO 3 3− molecule-ion in natural calcite

Electron paramagnetic resonance (EPR) spectra of CO ₃ ^3– molecule-ions stabilized by Sc³⁺ in natural calcite were identified and studied at X-band frequencies and room temperature. The principal values of the g-tensor (g _xx= 1.9997, g _yy = 2.0030, g _zz = 1.9972) and the direction cosines of the g and A tensors for CO ₃ ^3– -Sc³⁺ center were found to be close to that for the well-known CO ₃ ^3– -Y³⁺ center. A quantitative comparison of different impurity contents in calcite samples and analysis of the intensities of forbidden transitions were used to identify Sc³⁺. An estimation of the unpaired electron spin density on the nuclei of paramagnetic centers confirms that both centers, CO ₃ ^3– -Sc³⁺ and CO ₃ ^3– -Y³⁺, have the same nature.     

The elasticity of the upper mantle orthosilicates olivine and garnet to 3 GPa

The elastic moduli of single crystals of pyrope-rich garnet and San Carlos olivine have been measured over a 3 GPa pressure range at room temperature. The combination of improved ultrasonic techniques and this large pressure range provide for more reliable characterization of the pressure dependence of acoustic wave velocities than has previously been possible. First and second pressure derivatives of the velocities have been determined within 1 percent and 10 percent respectively. The Hashin-Shtrikman bounds for the pressure dependences of the bulk and shear moduli of the garnet used in this study are; K = 173.6 GPa, K = 4.93, K = –0.28 GPa^–1, G= 94.9 GPa, G = 1.56, G = –0.08 GPa^–1 and the Hashin-Shtrikman least-upper bounds and greatestlower bounds for the pressure dependences of the bulk and shear moduli of the San Carlos olivine are K=129.8 GPa, K = 4.66, K= –0.15 GPa^–1, G = 77.8 GPa, G = 1.93, G = –0.11 GPa^–1 and K = 129.2 GPa, K = 4.63, K= –0.15 GPa^–1 G = 77.3 GPa, G=1.96, G = –0.11 GPa^–1 respectively. The determination of the room-pressure elastic moduli of this pyrope-almandine garnet removes the previously observed anomaly in the predictions of systematic treatments of variations of the elastic moduli of garnets with composition. The determination of the second pressure derivatives of the moduli of garnet and olivine illustrates the importance of these terms in extrapolations to higher pressures — with K/P for these crystals being reduced by 17 percent and 9 percent respectively over the 3 GPa pressure range.     

Pressure and temperature dependence of the elastic properties of synthetic MnO

The adiabatic elastic stiffness constants of synthetic single-crystal MnO were measured in this study using pulse superposition interferometry. Data were obtained up to 1.0 GPa in pressure and over the temperature range 273 to 473 K. As a result, we were able to determine the complete set of second-order stiffness moduli (C _ij ^s ) and their pressure and temperature derivatives, as well as higher-order properties for selected modes. Relevant results for the adiabatic bulk modulus are: K ^s=155.1±0.8 GPa; (K^s/P)_T=4.70±0.13; and, (K ^s/T)_P= -0.0203±0.0009 GPa/K. Our results for the second-order moduli are generally consistent with the data from previous studies. However, relative to the estimated uncertainties, small and systematic discrepancies appear to characterize the data set. The available evidence indicates that the differences result from microstructural variations (in particular, microcracks and Mn₃O₄ inclusions) between the synthetic MnO specimens used in different investigations. The pure shear mode C ₄₄ exhibits anomalous soft-mode behavior with both temperature (the ambient derivative is positive) and pressure (the ambient derivative is negative). In both cases the C ₄₄ data trends appear to primarily reflect the influence of Mn-Mn magnetoelastic interactions associated with the onset of a paramagnetic-antiferromagnetic (PM AFM) phase transition.     

Equation of state,structural behaviour and phase diagram of synthetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as a function of pressure and temperature

The behaviour of synthetic Mg-ferrite (MgFe₂O₄) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K₀=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa^–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by _a0+_a1*(T–298)+_a2/(T–298)², where _a0=9.1(1) 10^–6 K^–1, _a1=4.9(2) 10^–9 K^–2 and _a2= 5.1(5) 10^–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol^–1 and =–17.6(± 1.2) kJ mol^–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe₂O₄, which shows that the high-pressure transition from spinel to orthorombic CaMn₂O₄-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe₂O₃.     

Compressional behaviour of CaNiSi2O6 clinopyroxene: bulk modulus systematic and cation type in clinopyroxenes

A single-crystal of composition CaNiSi₂O₆ (space group C2/c) was investigated at high pressure up to about 7.8 GPa by X-ray diffraction. The unit-cell parameters were measured at 18 different pressures. The P-V data were fitted by a third-order Birch-Murnaghan equation of state V₀=435.21(1) ų, K ₀=117.6(3) GPa and K^=6.4(1). The linear axial compressibilities _a, _b, _c and a sin are 2.14(1), 3.00(1), 2.43(1) and 1.63(1) × 10–3 GPa^–1. Comparing the compressibility data with other CaM1Si₂O₆ pyroxenes we suggest that the empirical K × V = constant relationships are followed in C2/c pyroxenes only if the same valence electron character is shared.     

P - V - T equation of state of stishovite to the mantle transition zone conditions

In-situ synchrotron X-ray diffraction experiments were conducted using the SPEED-1500 multi-anvil press of SPring-8 on stishovite SiO₂ and pressure-volume-temperature data were collected at up to 22.5 GPa and 1,073 K, which corresponds to the pressure conditions of the base of the mantle transition zone. The analysis of room-temperature data yielded V₀=46.56(1) ų, K_{T 0}=296(5) GPa and K _T =4.2(4), and these properties were consistent with the subsequent thermal equation of state (EOS) analyses. A fit of the present data to high-temperature Birch-Murnaghan EOS yielded (K_T /T) _P =–0.046(5) GPa K^–1 and = a + bT with values of a =1.26(11)×10^–5 K^–1 and b =1.29(17)×10^–8 K^–2. A fit to the thermal pressure EOS gives ₀=1.62(9)×10^–5 K^–1, ( K _T / T) _V =–0.027(4) GPa K^–1 and (²P /T ²) _V =27(5)×10^–7 GPa K^–2. The lattice dynamical approach by Mie-Grüneisen-Debye EOS yielded ₀=1.33(6), q =6.1(8) and ₀=1160(120) K. The strong volume dependence of the thermal pressure of stishovite was revealed by the analysis of present data, which was not detectable by the previous high-temperature data at lower pressures, and this yields ( K _T / T) _V 0 and q 1. The analyses for the fictive volume for a and c axes show that relative stiffness of c axis to a axis is similar both on compression and thermal expansion. Present EOS enables the accurate estimate of density of SiO₂ in the deep mantle conditions.     

31P solid-state nuclear magnetic resonance spectroscopy of aluminum phosphate minerals

This study examines the links between ³¹P solidstate NMR studies of aluminum phosphate minerals and their crystallographic structures. We found that ³¹P isotropic chemical shift values, _iso, carry little information about mineral structures. There seems to be no relation between the chemical shift anisotropy, =₃₃–₁₁ (₃₃>₂₂> ₁₁), and indicies of phosphate-tetrahedra distortion. ³¹P¹H heteronuclear magnetic dipole interactions, on the other hand, carry important information about hydrous phosphate mineral structures, information that should prove to be quite valuable in studies of phosphate adsorbed on mineral surfaces. This interaction can be measured through a variety of qualitative and quantitative experiments. It appears that spin diffusion is so rapid that subtle differences in hydrogen-bonding environments cannot be resolved.     

Unquenchable high-pressure perovskite polymorphs of MnSnO3 and FeTiO3

New high-pressure orthorhombic (GdFeO₃-type) perovskite polymorphs of MnSnO₃ and FeTiO₃ have been observed using in situ powder X-ray diffraction in a diamond-anvil cell with synchrotron radiation. The materials are produced by the compression of the lithium niobate polymorphs of MnSnO₃ and FeTiO₃ at room temperature. The lithium niobate to perovskite transition occurs reversibly at 7 GPa in MnSnO₃, with a volume change of -1.5%, and at 16 GPa in FeTiO₃, with a volume change of -2.8%. Both transitions show hysteresis at room temperature. For MnSnO₃ perovskite at 7.35 (8) GPa, the orthorhombic cell parameters are a=5.301 (2) A, b=5.445 (2) Å, c=7.690 (8) Å and V= 221.99 (15) ų. Volume compression data were collected between 7 and 20 GPa. The bulk modulus calculated from the compression data is 257 (18) GPa in this pressure region. For FeTiO₃ perovskite at 18.0 (5) GPa, cell parameters are a=5.022 (6) Å, b=5.169 (5) Å, c=7.239 (9) Å and V= 187.94 (36) ų. Based on published data on the quench phases, the FeTiO₃ perovskite breaks down to a rocksalt + baddelyite mixture of FeO and TiO₂ at 23 GPa. This is the first experimental verification of the pressure-induced breakdown of a perovskite to simple oxides.     

Pressure-volume-temperature behavior of γ-Fe2SiO4 (spinel) based on static compression measurements at 400° C

Thirteen energy-dispersive x-ray diffraction spectra for -Fe₂SiO₄ (spinel) collected in situ at 400° C and pressures to 24 GPa constitute the basis for an elevated-temperature static compression isotherm for this important high-pressure phase. A Murnaghan regression of these molar volume measurements yields 177.3 (±17.4) GPa and 5.4(±2.5) for the 400° C, room pressure values of the isothermal bulk modulus (K _{P 0}) and its first pressure derivative (K _{P 0}), respectively. When compared to the room-Tdeterminations of K _{P 0} available in the literature, our 400° C K _{P 0} yields -4.1 (±6.2)×10^-2 GPa/degree for the average value of (K/T) _{P 0} over the temperature interval 25° C<><400°>A five-parameter V(P, T) equation for -Fe₂SiO₄ based on simultaneous regression of our data combined with the elevated P-Tdata of Yagi et al. (1987) and the extrapolated thermal expansion values from Suzuki et al. (1979) yields isochores which have very little curvature [(² T/P ²) _v 0], in marked contrast to the isochores for fayalite (Plymate and Stout 1990) which exhibit pronounced negative curvature [(T/P ²) _v <0]. along=" the=">-Fe₂SiO₄ reaction boundary V_Rvaries from a minimum of approximately 8.3% at approximately 450° C to approximately 8.9% at 1200° C. Extrapolation of the fayalite and -Fe₂SiO₄ V(P, T) relationships to the temperature and pressure of the 400 km discontinuity suggests a V _R of approximately 8.4% at that depth, approximately 10% less than the 9.3% V _R at ambient conditions.     

Koritnigit,Zn[H2O|HOAsO3], ein neues Mineral aus Tsumeb,Südwestafrika

Zusammenfassung Das neue Mineral Koritnigit ist ein wasserhaltiges Zinkhydrogenarsenat der Formel Zn[H₂O|HOAsO₃]. Die chemische Analyse (Elektronenmikrosonde und T.G.A.) ergab: As₂O₅ 51,75%, ZnO 35,97% und H₂O 12,3%, Summe 100,0%. Die HOAsO₃-Ionen wurden IR-spektroskopisch nachgewiesen. Koritnigit ist löslich in kalter, verdünnter HCl und HNO₃.Die Gitterkonstanten sind:a ₀=7,948(2),b ₀=15,829(5),c ₀=6,668(2) Å, =90,86(2), =96,56(2), =90,05(2)^o,V=833,2(4)ų,V=8. Die Raumgruppe ist . Die stärksten Linien des Pulverdiagramms sind: 7,90(10) (020,100), 3,83(7) ( ), 3,16(9) ( ) 2,926(4) (150), 2,679(4) ( ), 2,461(6) ( ), 2,186(5) ( ), 1,969(4) (400), 1,649(3) (004).Koritnigit ist wasserklar bis durchscheinend weiß. Idiomorphe Kristalle sind nicht bekannt. Die Spaltbarkeit nach {010} ist ausgezeichnet und auf {010} sind Spaltspuren nach [001] und nach [100] erkennbar. Härte 2.G=3,54 g·cm^–3,D _x =3,56 g·cm^–3. Koritnigit ist optisch zweiachsig positiv, 2V70(5)^o. Die Werte der Lichtbrechung sind:n =1,632(5),n =1,652(3) undn =1,693(3).Koritnigit wurde auf der 31. Sohle der Tsumeb-Mine, Südwestafrika gefunden. Er kommt als Sekundärmineral in Paragenese mit Cu-Adamin, Stranskiit und drei weiteren, vorerst nicht identifizierten mineralen in Zersetzungshohlräumen von Tennantit vor.

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Koritnigite, Zn[H₂O|HOAsO₃], a new mineral from Tsumeb, South West Africa

Summary The new mineral koritnigite is a hydrated zinc hydrogen arsenate with the formula Zn[H₂O|HOAsO₃]. Chemical analysis (electron microprobe and t.g.a.) gave: As₂O₅ 51.75%, ZnO 35.97%, and H₂O 12.3%, total 100.0%. The HOAsO₃ ions were determined by IR spectroscopy. Koritnigite is soluble in cold diluted HCl and HNO₃. The unit cell dimensions are:a ₀=7.948(2),b ₀=15.829(5),c ₀=6.668(2)Å, =90.86(2), =96.56(2), =90.05(2)^o,V=833.2(4) ų,Z=8. The space group is . The strongest lines of the powder pattern are: 7.90(10) (020, 100), 3.83(7) ( ), 3.16(9) ( ), 2.926(4) (150), 2.679(4) ( ), 2.461(6) ( ), 2.186(5) ( ), 1.969(4)(400), 1.649(3) (004).

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Herrn Univ. Prof. Dr.H. Meixner zum 70. Geburtstag gewidmet.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written:     

Thermodynamic properties of strontianite-witherite solid solution (Sr,Ba)CO3

Structural parameters and thermodynamic properties of strontianite — witherite solid solutions have been studied by X-ray powder diffraction, heat flux Calvet calorimetry and cation-exchange equilibria technique. X-ray study of the synthetic samples have shown linear and quadratic (for c-parameter) composition dependencies of the lattice constants in the carbonate solid solution. The thermodynamic energy parameters demonstrate the non-ideal character of strontianite — witherite solid solutions. Enthalpies of solution of the samples have been measured in 2PbO*B₂O₃ at 973 K. The new data on the enthalpy of formation H _f,298.15 ⁰ of SrCO₃ and BaCO₃ were obtained: -1231.4±3.2 and -1209.9±5.8 kJ*mol^-1 respectively. The enthalpy of mixing of the solid solution was found to be positive and asymmetric with maximum at X_Ba (carbonate)=0.35. The composition dependence of the enthalpy of mixing may be described by two — parametric Margules model equation: H _mix=X _BaX _Sr[(4.40±3.91)X _Ba+(28.13±3.91)X _Sr] kJmol^–1 Cation-exchange reactions between carbonates and aqueous SrCl₂-BaCl₂ supercritical solutions (fluids) were carried out at 973 and 1073 K and 2 kbar. Calculated Margules model parameters of the excess free energy are: for orthorhombic carbonate solid solutions W _Sr=W _Ba=11.51±0.40 kJmol^–1 (973 K) and W _Sr=W _Ba=12.09±0.95 kJmol^– (1073 K) for trigonal carbonate solid solutions W _Sr=W _Ba=13.55±0.40 kJmol^– (1073 K).     

High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

Equation of state of iron–silicon alloys to megabar pressure

The stability and pressure–volume equation of state of iron–silicon alloys, Fe-8.7 wt% Si and Fe-17.8 wt% Si, have been investigated using diamond-anvil cell techniques up to 196 and 124 GPa, respectively. Angular–dispersive X-ray diffractions of iron–silicon alloys were measured at room temperature using monochromatic synchrotron radiation and an imaging plate (IP). A bcc–Fe-8.7 wt% Si transformed to hcp structure at around 1636 GPa. The high-pressure phase of Fe-8.7 wt% Si with hexagonal close-packed (hcp) structure was found to be stable up to 196 GPa and no phase transition of bcc–Fe-17.8 wt% Si was observed up to 124 GPa. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state (BM EOS) with zero–pressure parameters: V₀=22.2(8) ų, K₀=198(9) GPa, and K₀=4.7(3) for hcp–Fe-8.7 wt% Si and V₀=179.41(45) ų, K₀=207(15) GPa and K₀=5.1(6) for Fe-17.8 wt% Si. The density and bulk sound velocity of hcp–Fe-8.7 wt% Si indicate that the inner core could contain 3–5 wt% Si.     

Johillerit,Na(Mg,Zn)3 Cu(AsO4)3, ein neues Mineral aus Tsumeb,Namibia

Zusammenfassung Die chemische Analyse des neuen Minerals Johillerit mit der Elektronenmikrosonde ergab: Na₂O 5,4, MgO 18,3, ZnO 5,4, CuO 15,8 und As₂O₅ 55,8, Summe 100.7%. Aus diesem Ergebnis wurde die idealisierte Formel Na(Mg, Zn)₃ Cu(AsO₄)₃ abgeleitet. Johillerit ist monoklin mit der RaumgruppeC2/c. Die Gitterkonstanten sind:a=11,870 (3),b=12,755 (3),c=6,770 (2) , =113,42 (2)°,Z=4. Die stärksten Linien des Pulverdiagramms sind: 4,06 (5) (22 ), 3,50 (4) (310), 3,25 (8) (11 ), 2,75 (10) (330, 240), 2,64 (5) (311, 13 , 40 ), 1,952 (4) (13 , 35 ), 1,682 (4) (20 , 460), 1,660 (5) (40 , 71 , 550, 64 ), 1,522 (4) (442, 153, 13 ). Es bestehen enge strukturelle Beziehungen zwischen Johillerit und O'Danielit, Na(Zn, Mg)₃H₂(AsO₄)₃, sowie einigen synthetischen. Verbindungen.Johillerit ist violett durchscheinend. Die Spaltbarkeit nach {010} ist ausgezeichnet und nach {100} und {001} gut.H (Mohs)3.D=4,15 undD _X =4,21 g·cm^–3. Das Mineral ist optisch zweiachsig positiv, 2V80 (5)°. Die Werte der Lichtbrechung sindn =1,715 (4),n =1,743 (4) undn =1,783 (4). Die Auslöschung istn b und auf (010)n c16°. Johillerit ist stark pleochroitisch mit den AchsenfarbenX=violett-rot,Y = blauviolett undZ = grünblau. Das neue Mineral kommt in radialstrahligen Massen gemeinsam mit kupferhaltigem Adamin und Konichalcit in zersetzem Kupfererz von Tsumeb, Namibia, vor. Die Benennung erfolgte nach Prof. Dr.J.-E. Hiller (1911–1972).

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Johillerite, Na(Mg, Zn) ₃ Cu(AsO ₄ ) ₃ , a new mineral from Tsumeb, Namibia

Summary Electron microprobe analysis of the new mineral johillerite gave Na₂O 5.4, MgO 18.3, ZnO 5.4, CuO 15.8, and As₂O₅ 55.8, total 100.7%. From this result, the ideal formula is given as Na(Mg, Zn)₃ Cu(AsO₄)₃. Johillerite crystallizes monoclinic,C2/c. The unit cell dimensions are:a=11.870(3),b=12.755 (3),c=6.770 (2) , =113.42 (2)°,Z=4. The strongest lines on the X-ray powder diffraction pattern are: 4,06 (5) (22 ), 3,50 (4) (310), 3,25 (8) (11 ), 2,75 (10) (330, 240), 2,64 (5) (311, 13 , 40 ), 1,952 (4) (13 , 35 ), 1,682 (4) (20 , 460), 1,660 (5) (40 , 71 , 550, 64 ), 1,522 (4) (442, 153, 13 ). There is a close relationship between johillerite, o'danielite, Na(Zn, Mg)₃H₂(AsO₄)₃, and some synthetic compounds. Johillerite is violet in colour, transparent. Cleavage is {010} perfect, {100} and {001} good.H (Mohs)3.D=4.15 andD _X =4.21 g·cm^–3. The mineral is optically biaxial positive, 2V80 (5)°. The refractive indices are:n =1.715 (4),n =1.743 (4),n =1.783 (4). The extinction isn b and on (010)n c16°. Strongly pleochroic with axial coloursX=violet-red,Y=bluish violet andZ=greenish blue. The new mineral was found in radiated masses together with cuprian adamite and conichalcite in an oxidized copper ore from Tsumeb, Namibia. It is named in honour of Prof. Dr.J.-E. Hiller (1911–1972).

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