Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

Pressure induced phase transition in Pb<Subscript>6</Subscript>Bi<Subscript>2</Subscript>S<Subscript>9</Subscript>

The crystal structure of Pb₆Bi₂S₉ is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb₆Bi₂S₉ at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb²⁺ and Bi³⁺ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb₆Bi₂S₉, is solved in Pna2 ₁ (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb₃Bi₂S₆ (lillianite).     

Hydrogen bond effects on compressional behavior of isotypic minerals: high-pressure polymorphism of cristobalite-like Be(OH)<Subscript>2</Subscript>

Three isotypic crystals, SiO₂ (α-cristobalite), ε-Zn(OH)₂ (wülfingite), and Be(OH)₂ (β-behoite), with topologically identical frameworks of corner-connected tetrahedra, undergo displacive compression-driven phase transitions at similar pressures (1.5–2.0 GPa), but each transition is characterized by a different mechanism resulting in different structural modifications. In this study, we report the crystal structure of the high-pressure γ-phase of beryllium hydroxide and compare it with the high-pressure structures of the other two minerals. In Be(OH)₂, the transition from the ambient β-behoite phase with the orthorhombic space group P2₁2₁2₁ and ambient unit cell parameters a = 4.5403(4) Å, b = 4.6253(5) Å, c = 7.0599(7) Å, to the high-pressure orthorhombic γ-polymorph with space group Fdd2 and unit cell parameters (at 5.3(1) GPa) a = 5.738(2) Å, b = 6.260(3) Å, c = 7.200(4) Å takes place between 1.7 and 3.6 GPa. This transition is essentially second order, is accompanied by a negligible volume discontinuity, and exhibits both displacive and reversible character. The mechanism of the phase transition results in a change to the hydrogen bond connectivities and rotation of the BeO₄ tetrahedra.     

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.     

Compressibility of strontium orthophosphate Sr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> at high pressure

High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr₃(PO₄)₂ has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V ₀ = 498.0 ± 0.1 Å³, an isothermal bulk modulus of K _T  = 89.5 ± 1.7 GPa, and first pressure derivative of K _T ′ = 6.57 ± 0.34. If K _T ′ is fixed at 4, K _T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K _c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO₄ vibrations of Sr₃(PO₄)₂ is calculated to be 0.30(2).     

Thermoelastic properties of chromium oxide Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> (eskolaite) at high pressures and temperatures

A new synchrotron X-ray diffraction study of chromium oxide Cr₂O₃ (eskolaite) with the corundum-type structure has been carried out in a Kawai-type multi-anvil apparatus to pressure of 15 GPa and temperatures of 1873 K. Fitting the Birch–Murnaghan equation of state (EoS) with the present data up to 15 GPa yielded: bulk modulus (K _0,T0), 206 ± 4 GPa; its pressure derivative K′_0,T , 4.4 ± 0.8; (?K _0,T /?T) = ?0.037 ± 0.006 GPa K^?1; a = 2.98 ± 0.14 × 10^?5 K^?1 and b = 0.47 ± 0.28 × 10^?8 K^?2, where α _0,T  = a + bT is the volumetric thermal expansion coefficient. The thermal expansion of Cr₂O₃ was additionally measured at the high-temperature powder diffraction experiment at ambient pressure and α _0,T0 was determined to be 2.95 × 10^?5 K^?1. The results indicate that coefficient of the thermal expansion calculated from the EoS appeared to be high-precision because it is consistent with the data obtained at 1 atm. However, our results contradict α ₀ value suggested by Rigby et al. (Brit Ceram Trans J 45:137–148, 1946) widely used in many physical and geological databases. Fitting the Mie–Grüneisen–Debye EoS with the present ambient and high-pressure data yielded the following parameters: K _0,T0 = 205 ± 3 GPa, K′_0,T  = 4.0, Grüneisen parameter (γ ₀) = 1.42 ± 0.80, q = 1.82 ± 0.56. The thermoelastic parameters indicate that Cr₂O₃ undergoes near isotropic compression at room and high temperatures up to 15 GPa. Cr₂O₃ is shown to be stable in this pressure range and adopts the corundum-type structure. Using obtained thermoelastic parameters, we calculated the reaction boundary of knorringite formation from enstatite and eskolaite. The Clapeyron slope (with \({\text{d}}P/{\text{d}}T = - 0.014\) GPa/K) was found to be consistent with experimental data.     

Structural investigations of (Ca,Sr)ZrO<Subscript>3</Subscript> and Ca(Sn,Zr)O<Subscript>3</Subscript> perovskite compounds

(Ca _x ,Sr_1?x )ZrO₃ and Ca(Sn _y ,Zr_1-y )O₃ solid solutions were synthesized by solid-state reaction at high temperature before to be studied by powder X-ray diffraction and Raman Spectroscopy. Diffraction data allow the distortion of the ABO₃ perovskite structure to be investigated according to cations substitution on A and B-sites. It is shown that distortion, characterized by Φ, the tilt angle of BO₆ octahedra, slightly increases with decreasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds and strongly decreases with decreasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds. Such results are discussed in view of the relative A and B cation sizes. Raman data show that vibrational spectra are strongly affected by the cation substitution on A-site; the frequencies of most vibrational modes increase with increasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds, i.e. with the decreasing mean size of the A-cation; the upper shift is observed for the 358 cm^?1 mode (?ν/?r = ?60.1 cm^?1/Å). On the other hand, the cation substitution on B-sites, slightly affect the spectra; it is shown that in most cases, the frequency of vibrational modes increases with increasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds, i.e. with the decreasing mean size of the B-cation, but that two modes (287 and 358 cm^?1) behave differently: their frequencies decrease with the decreasing mean size of the B-cation, with a shift respectively equal to +314 and +162 cm^?1/Å. Such results could be used to predict the location of different elements such as trivalent cations or radwaste elements on A- or B-site, in the perovskite structure.     

Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.     

The thermal expansion and crystal structure of mirabilite (Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·10D<Subscript>2</Subscript>O) from 4.2 to 300 K,determined by time-of-flight neutron powder diffraction

We have collected high resolution neutron powder diffraction patterns from Na₂SO₄·10D₂O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P2₁/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å³ at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å³ at 300 K. Structures were refined to R _P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10^?7 T ³ + 0.00047(2) T² ? 0.027(2) T + 1437.0(1) Å³ (R ² = 99.98%). The coefficient of volume thermal expansion, α _V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α _V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.     

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.     

Crystal chemistry of selenates with mineral-like structures: VIII. Butlerite chains in the structure of K(UO<Subscript>2</Subscript>)(SeO<Subscript>4</Subscript>)(OH)(H<Subscript>2</Subscript>O)

A new potassium uranyl selenate compound K(UO₂)(SeO₄)(OH)(H₂O) has been synthesized for the first time using the technique of evaporation from water solution. Its crystal structure has been solved by direct methods (monoclinic, P2₁/c,a = 8.0413(9) Å, b = 8.0362(9) Å, c = 11.6032(14) Å, β = 106.925(2)°, V = 717.34(14) ų) and refined to R ₁ = 0.0319 (wR ₂ = 0.0824) for 1285 reflections with |F ₀| > 4σ _F . The structure consists of [(UO₂(SeO₄)(OH)(H₂O)]^? chains extending along axis b. In the chains, the uranyl pentagonal bipyramids are linked via bridged hydroxyl anions and tetrahedral oxoanions [SeO₄]^2?. Potassium ions are situated between these chains. No chains of that type have been observed in uranyl compounds earlier, but they had been detected in the structures of butlerite, parabutlerite, uklonskovite, fibroferrite, and a number of synthetic compounds.     

<Emphasis Type="Italic">P</Emphasis>–<Emphasis Type="Italic">V</Emphasis>–<Emphasis Type="Italic">T</Emphasis> equation of state of CaAl<Subscript>4</Subscript>Si<Subscript>2</Subscript>O<Subscript>11</Subscript> CAS phase

The thermoelastic parameters of the CAS phase (CaAl₄Si₂O₁₁) were examined by in situ high-pressure (up to 23.7 GPa) and high-temperature (up to 2,100 K) synchrotron X-ray diffraction, using a Kawai-type multi-anvil press. P–V data at room temperature fitted to a third-order Birch–Murnaghan equation of state (BM EOS) yielded: V _0,300 = 324.2 ± 0.2 Å³ and K _0,300 = 164 ± 6 GPa for K′ _0,300 = 6.2 ± 0.8. With K′ _0,300 fixed to 4.0, we obtained: V _0,300 = 324.0 ± 0.1 Å³ and K _0,300 = 180 ± 1 GPa. Fitting our P–V–T data with a modified high-temperature BM EOS, we obtained: V _0,300 = 324.2 ± 0.1 Å³, K _0,300 = 171 ± 5 GPa, K′ _0,300 = 5.1 ± 0.6 (?K _0,T /?T) _P  = ?0.023 ± 0.006 GPa K^?1, and α_0,T  = 3.09 ± 0.25 × 10^?5 K^?1. Using the equation of state parameters of the CAS phase determined in the present study, we calculated a density profile of a hypothetical continental crust that would contain ~10 vol% of CaAl₄Si₂O₁₁. Because of the higher density compared with the coexisting minerals, the CAS phase is expected to be a plunging agent for continental crust subducted in the transition zone. On the other hand, because of the lower density compared with lower mantle minerals, the CAS phase is expected to remain buoyant in the lowermost part of the transition zone.     

Thermal equation of state of CaIrO<Subscript>3</Subscript> post-perovskite

The pressure–volume–temperature (P–V–T) relation of CaIrO₃ post-perovskite (ppv) was measured at pressures and temperatures up to 8.6 GPa and 1,273 K, respectively, with energy-dispersive synchrotron X-ray diffraction using a DIA-type, cubic-anvil apparatus (SAM85). Unit-cell dimensions were derived from the Le Bail full profile refinement technique, and the results were fitted using the third-order Birth-Murnaghan equation of state. The derived bulk modulus \( K_{T0} \) at ambient pressure and temperature is 168.3 ± 7.1 GPa with a pressure derivative \( K_{T0}^{\prime } \) = 5.4 ± 0.7. All of the high temperature data, combined with previous experimental data, are fitted using the high-temperature Birch-Murnaghan equation of state, the thermal pressure approach, and the Mie-Grüneisen-Debye formalism. The refined thermoelastic parameters for CaIrO₃ ppv are: temperature derivative of bulk modulus \( (\partial K_{T} /\partial T)_{P} \) = ?0.038 ± 0.011 GPa K^?1, \( \alpha K_{T} \) = 0.0039 ± 0.0001 GPa K^?1, \( \left( {\partial K_{T} /\partial T} \right)_{V} \) = ?0.012 ± 0.002 GPa K^?1, and \( \left( {\partial^{2} P/\partial T^{2} } \right)_{V} \) = 1.9 ± 0.3 × 10^?6 GPa² K^?2. Using the Mie-Grüneisen-Debye formalism, we obtain Grüneisen parameter \( \gamma_{0} \) = 0.92 ± 0.01 and its volume dependence q = 3.4 ± 0.6. The systematic variation of bulk moduli for several oxide post-perovskites can be described approximately by the relationship K _T0  = 5406.0/V(molar) + 5.9 GPa.     

High-pressure synthesis,long-term stability of single crystals of diboron trioxide,B<Subscript>2</Subscript>O<Subscript>3</Subscript>, and an empirical electronic polarizability of <Superscript>[3]</Superscript>B<Superscript>3+</Superscript>

Single crystals of B₂O₃ are needed for the precise determination of the refractive indices used to calculate the electronic polarizability α of 3-coordinated boron. The α(B) values in turn are used to predict mean refractive indices of borate minerals. Since the contribution of boron to the total polarizability of a mineral is very low, the synthetic compound B₂O₃ represents an ideal model system because of its high molar content of boron. Millimeter-sized crystals were synthesized at 1 GPa in a piston-cylinder apparatus. The samples were heated above the liquidus (800 °C), subsequently cooled at 15 °C/h to 500 °C and finally quenched. The refractive indices were determined by the immersion method using a microrefractometer spindle stage. The refractive indices n _o = 1.653 (3) and n _e = 1.632 (3) correspond to a total polarizability for B₂O₃ of α = 4.877 Å³. These values were used to determine the electronic polarizability of boron of α(B) = 0.16 Å³. Although the surface of the B₂O₃ crystals was coated with a hydrous film immediately after being exposed to air, its bulk crystallinity is retained for a period of at least 2 months.     

The crystal structure and thermal expansion tensor of MgSO<Subscript>4</Subscript>–11D<Subscript>2</Subscript>O(meridianiite) determined by neutron powder diffraction

We have collected high-resolution neutron powder diffraction patterns from MgSO₄·11D₂O over the temperature range 4.2–250 K. The crystal is triclinic, space-group \( \text{P} \bar{1} \) (Z = 2) with a = 6.72746(6) Å, b = 6.78141(6) Å, c = 17.31803(13) Å, α = 88.2062(6)°, β = 89.4473(8)°, γ = 62.6075(5)°, and V = 701.140(6) ų at 4.2 K, and a = 6.75081(3) Å, b = 6.81463(3) Å, c = 17.29241(6) Å, α = 88.1183(3)°, β = 89.4808(3)°, γ = 62.6891(3)°, and V = 706.450(3) ų at 250 K. Structures were refined to wRp = 3.99 and 2.84% at 4.2 and 250 K, respectively. The temperature dependence of the lattice parameters over the intervening range have been fitted with a modified Einstein oscillator model which was used to obtain the coefficients of the thermal expansion tensor. The volume thermal expansion, α_V, is considerably smaller than ice Ih at all temperatures, and smaller even than MgSO₄·7D₂O (although ?α_V/?T is very similar for both sulfates); MgSO₄·11D₂O exhibits negative α_V below 55 K (compared to 70 K in D₂O ice Ih and 20 K in MgSO₄·7D₂O) The relationship between the magnitude and orientation of the principal axes of the expansion tensor and the main structural elements are discussed.     

Hydrostatic compression of galenobismutite (PbBi<Subscript>2</Subscript>S<Subscript>4</Subscript>): elastic properties and high-pressure crystal chemistry

A single-crystal sample of galenobismutite was subjected to hydrostatic pressures in the range of 0.0001 and 9 GPa at room temperature using the diamond-anvil cell technique. A series of X-ray diffraction intensities were collected at ten distinct pressures using a CCD equipped 4-circle diffractometer. The crystal structure was refined to R1(|F₀| > 4σ) values of approximately 0.05 at all pressures. By fitting a third-order Birch-Murnaghan equation of state to the unit-cell volumes V ₀ = 700.6(2) ų, K ₀ = 43.9(7) GPa and dK/dP = 6.9(3) could be determined for the lattice compression. Both types of cations in galenobismutite have stereochemically active lone electron pairs, which distort the cation polyhedra at room pressure. The cation eccentricities decrease at higher pressure but are still pronounced at 9 GPa. Galenobismutite is isotypic with CaFe₂O₄ (CF) but moves away from the idealised CF-type structure during compression. Instead of the two octahedral cation sites and one bi-capped trigonal-prismatic site, PbBi₂S₄ attains a new high-pressure structure characterised by one octahedral site and two mono-capped trigonal-prismatic sites. Analyses of the crystal structure at high pressure confirm the preference of Bi for the octahedral site and the smaller one of the two trigonal-prismatic sites.     

The crystal structure of alumoklyuchevskite,K<Subscript>3</Subscript>Cu<Subscript>3</Subscript>AlO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript>

The crystal structure of the unstable mineral alumoklyuchevskite K₃Cu₃AlO₂(SO₄)₄ [monoclinic, I2, a = 18.772(7), b = 4.967(2), c = 18.468(7) Å, β = 101.66(1)°, V = 1686(1) Å] was refined to R ₁ = 0.131 for 2450 unique reflections with F ≥ 4σF _hkl. The structure is based on oxocentered tetrahedrons (OAlCu ₃ ⁷⁺ ) linked into chains via edges. Each chain is surrounded by SO₄ tetrahedrons forming a structural complex. Each complex is elongated along the b axis. This type of crystal structure was also found in other fumarole minerals of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka Peninsula, Russia, 1975–1976), klyuchevskite, K₃Cu₃Fe³⁺O₂(SO₄)₄; and piypite, K₂Cu₂O(SO₄)₂.     

Crystal chemistry of natural and synthetic lead oxyhalides. Part I. Crystal structure of Pb<Subscript>13</Subscript>O<Subscript>10</Subscript>Cl<Subscript>6</Subscript>

Crystals of lead oxychloride Pb₁₃O₁₀Cl₆ have been synthesized on the basis of high-temperature solid-state reactions. The Pb₁₃O₁₀Cl₆ structure was studied using X-ray single-crystal diffraction analysis. The compound is monoclinic, and the space group is C2/c; the unit-cell dimensions are a = 16.1699(14), b = 7.0086(6), c = 23.578(2) Å, β = 97.75°, and V = 2647.6(4) ų. The structure has been solved by direct methods and refined to R ₁ = 0.0505 for 2671 observed unique reflections. The structure is a 3D framework consisting of OPb₄ tetrahedrons. Chlorine atoms are located in the framework channels. The structure contains seven symmetrically independent Pb atoms, which are coordinated by 2 to 4 O^2? and 2 to 4 Cl^? anions. The synthesized compound is compared with other natural and synthetic lead oxyhalides.