(Na,Ca)(Ti3+,Mg)Si2O6-clinopyroxenes at high pressure: influence of cation substitution on elastic behavior and phase transition

A compressional study of (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxenes was carried out at high pressures between 10⁻⁴ and 10.2 GPa using in situ single-crystal X-ray diffraction, Raman spectroscopy and optical absorption spectroscopy. Compressional discontinuities accompanied by structural changes, in particular, the appearance of two distinct Ti³⁺–Ti³⁺ distances within the octahedral chains at 4.37 GPa, provide evidence for the occurrence of a phase transition in NaTi³⁺Si₂O₆. Equation-of-state parameters are K ₀ = 115.9(7) GPa with K′ = −0.9(3) and K ₀ = 102.7(8) GPa with K′ = 4.08(5) for the low- and high-pressure range, respectively. The transition involves a C2/c–P [`1] \overline{1} symmetry change, which can be confirmed by the occurrence of new modes in Raman spectra. Since no significant discontinuity in the evolution of the unit-cell volume with pressure has been observed, the transition appears to be second-order in character. The influence of the coupled substitution Na⁺Ti³⁺↔Ca²⁺Mg²⁺ on the static compression behavior and the structural stability has been investigated using a sample of the intermediate composition (Na_0.54Ca_0.46)(Mg_0.46Ti_0.54)Si₂O₆. No evidence for a deviation from continuous compression behavior has been found, neither in lattice parameter nor in structural data and the fit of a third-order Birch–Murnaghan equation-of-state to the pressure–volume data yields a bulk modulus of K ₀ = 109.1(5) GPa and K′ = 5.02(13). Raman and polarized absorption spectra have been compared to NaTiSi₂O₆ and reveal major similarities. The main driving force for the phase transition in NaTi³⁺Si₂O₆ is the localization of the Ti³⁺ d-electron and the accompanying distortion, which is suppressed in the (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxene.     

Thermal phase transition of potassium sulfate,K2SO4

The thermal phase transition of K₂SO₄ has been investigated by high temperature polarized light microscopy. K₂SO₄ undergoes a first-order transition at 587° C where the orthorhombic low temperature form (Pmcn) transforms into a hexagonal high temperature modification (P6₃/mmc). Prior to the beginning of the phase transition, K₂SO₄ shows an anomalous optical behavior. The crystal apparently becomes optically uniaxial twice at 338° and 425° C, respectively, and truly optically uniaxial at 587° C. The phase transition propagates through an intermediate temperature form, which is sandwiched between the low and the high temperature forms and moves in a definite direction, 〈130〉 (orthorhombic indices), in the vicinity of the phase transition. Passing through the phase transition point on cooling, dark belts crossing each other are observed which are a result of the transformation twins parallel to {110} and {130}.     

Structural change associated with the incommensurate-normal phase transition in akermanite, Ca2MgSi2O7, at high pressure

The structural changes associated with the incommensurate (IC)-normal (N) phase transition in akermanite have been studied with high-pressure single-crystal X-ray diffraction up to 3.79?GPa. The IC phase, stable at room pressure, transforms to the N phase at ～1.33?GPa. The structural transformation is marked by a small but discernable change in the slopes of all unit-cell parameters as a function of pressure. It is reversible with an apparent hysteresis and is classified as a tricritical phase transition. The linear compressibility of the a and c axes are 0.00280(10) and 0.00418(6)?GPa^?1 for the IC phase, and 0.00299(11) and 0.00367(8)?GPa^?1 for the N phase, respectively. Weighted volume and pressure data, fitted to a second-order Birch-Murnaghan equation of state (K′≡4.0), yield V₀=307.4(1)?ų and K₀=100(3)?GPa for the IC phase and V₀=307.6(2)?ų and K₀=90(2)?GPa for the N phase. No significant discontinuities in Si–O, Mg–O and Ca–O distances were observed across the transition, except for the Ca–O1 distance, which is more compressible in the IC phase than in the N phase. From room pressure to 3.79?GP the volume of the [SiO₄] tetrahedron is unchanged (2.16?ų), whereas the volumes of the [MgO₄] and [CaO₈] polyhedra decrease from 3.61 to 3.55(1)?ų and 32.8 to 30.9(2)?ų, respectively. Intensities of satellite reflections are found to vary linearly with the isotropic displacement parametr of Ca and the librational amplitude of the [SiO₄] tetrahedron. At room pressure, there is a mismatch between the size of the Ca cations and the configuration of tetrahedral sheets, which appears to be responsible for the formation of the modulated structure; as pressure increases, the misfit is diminished through the relative rotation and distortion of [MgO₄] and [SiO₄] tetrahedra and the differential compression of individual Ca–O distances, concurrent with a displacement of Ca along the (110) mirror plane toward the O1 atom. We regard the high-pressure normal structure as a result of the elimination of microdomains in the modulated structure.     

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.     

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

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

Zur Kristallstruktur des Noseans,Na8[SO4(Si6Al6O24)]1

Zusammenfassung Die Struktur des Noseans wurde mit dreidimensionalen Daten verfeinert. Hierbei ist die Verteilung der SO₄-Gruppen, der Na-Atome sowie die Position der SO₄-Sauerstoffe besonders berücksichtigt worden.Da eine Reihe von Reflexen diffuse Streaks aufweisen, deren Intensität sich durch Tempern merklich verringert, wurden die Daten eines getemperten Kristalls gesammelt. Es konnte nur der geordnete Teil der Struktur erfaßt werden, da ausschließlich die Peak-Intensitäten der Hauptreflexe der Messung zugrunde lagen.Es ergab sich, daß die Na-Atome wahrscheinlich zwei Möglichkeiten der Anordnung innerhalb der Struktur einnehmen und die Sauerstoffe der SO₄-Gruppe eine Reihe energetisch ähnlicher Plätze besetzen.Die verfeinerten Atomparameter werden mitgeteilt.

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Summary The structure of nosean (noselite) has been refined on the basis of 3-dimensional X-ray data with special interest in the SO₄-group distribution and the atomic positions of Na-ions and SO₄-oxygens.Some reflections show diffuse streaks that markedly can be weakened by heat treatment. The peak intensities of a heated crystal were measured and gave the ordered part of the structure.There probably exist two arrangements of the Na-ions and several equivalent configurations of the SO₄-oxygens.The refined values of the atomic parameters are given.

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Mit 4 Textabbildungen

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Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet     

Thermodynamic Calculation of Solubility of Na2SO4/K2SO4 in Hydrothermal Fluids

Sulfate fluids are common fluids in nature, and their salinity studies can provide important information for the evolution of ore-forming fluids, migration and enrichment of ore-forming elements, and the classification of deposit types. Considerable research has been carried out to investigate the solubility of Na₂SO₄ and K₂SO₄ in hydrothermal fluids, however most of the literature reported experimental data were under saturated vapor pressure or the water supercritical region. A few data have been reported for the low temperature hydrothermal mineralization region. Thermodynamic model is a useful method to study the properties of hydrothermal geofluids, especially for mineral solubility. Pitzer interaction model is one of the most widely used model to calculate the thermodynamic properties of hydrothermal fluids, but few work have ever been carried out to calculate the solubility of sulfate at high temperature and pressure. With Pitzer specific interaction model, using the literature reported density data of Na₂SO₄ and K₂SO₄ solutions at high temperature and pressure, the pressure effect on Pitzer activity coefficient of sulfate and the standard partial molar volume change during sulfate dissolution process were evaluated and related parameters were obtained. The standard partial molar volumes of Na₂SO₄ and K₂SO₄ calculated with these parameters agreed well with those reported in the literature. Combined with the relevant parameters in the literature under saturated vapor pressure, a thermodynamic model for Na₂SO₄ and K₂SO₄ solubility calculation with temperature up to 250 ℃ and pressure up to 40 MPa was developed. The model gave very good agreement with the experimental solubility data. With this model, Na₂SO₄ and K₂SO₄ solubility was calculated at high temperature and pressure. The calculation results showed that pressure had a positive effect on both the average activity coefficient and solubility product of Na₂SO₄ and K₂SO₄, but the solubility of Na₂SO₄ and K₂SO₄ decreased with pressure due to the larger change of the average activity coefficient with pressure. And as the temperature increased, the degree of such reduction became larger. The results herein can provide instructions for the compositional analysis of sulfate fluid inclusions.     

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

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

Structural variation in Ca(TixSi1−x)O3 perovskites (1>x>0.65) and the ordered phase Ca2TiSiO6

High pressure perovskites in the system CaTiO₃?CaSiO₃ in the composition range from 0 to 50% CaSiO₃ have been re-examined using powder x-ray diffraction, Raman spectroscopy, and transmission electron microscopy. In runs performed at 9 GPa and 1200 °C, a solid solution is obtained with compositions ranging from CaTiO₃ to near Ca(Ti_0.65Si_0.35)O₃, and with the orthorhombic distortion in the CaTiO₃ end-member diminishing to pseudocubic for Ca(Ti_0.65Si_0.35)O₃. Raman spectra show intensity changes and band broadening which are attributed to the reduction of orthorhombic character, but still indicate lower than cubic symmetry for the entire solid solution range. An ordered intermediate, Ca₂TiSiO₆, has been recovered from a run at 14 GPa at 1200 °C. The space group is Fm3m, with a=7.410(2)?Å, and the compound has the double perovskite structure. In this structure, Si-rich octahedral sites and Ti-rich octahedral sites alternate along the three principal axes. Transmission electron microscopy confirms the presence of the Fm3m ordered structure, and also documents the presence of lesser amounts of at least three other ordered perovskite structures which are not resolved in the x-ray data. These may account for extra features observed in the Raman spectrum which are inconsistent with mode assignments for the Fm3m phase. Non face-centered ordering schemes for these regions are suggested based on modeling of the HRTEM patterns.     

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

Ternesite, Ca5(SiO4)2SO4, a new mineral from the Ettringer Bellerberg/Eifel, Germany

Summary The new mineral ternesite, Ca₅(SiO₄)₂SO₄, has been found at the Ettringer Bellerberg near Mayen, Eifel, Germany. The crystal structure, already known from the synthetic analogue, was refined from single crystal X-ray data: orthorhombic, space group Puma with a= 6.863(1)Å, b=15.387(2) Å, c=10.181(1) Å Z=4, R=0.058, R_w=0.046 for 820 unique reflections with F₀> 3(F₀) and 96 variable parameters. The strongest peaks in the powder pattern are (d-value (Å),I, hkl): 2.830, 100, (033)/2.853, 63, (230)/2.565, 55, (060)/3.198, 42, (132)/1.892, 39, (035) + (125). The mineral is optically biaxial negative with refractive indices n_x = 1.630(1) (parallel [100]), ny = 1.637(2) (parallel [001]), and n_z = 1.640(1) (parallel [010]). The optical angle 2V_x was measured as 63.5(5)°.

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Ternesit, Ca₅(SiO₄)₂SO₄, ein neues Mineral vom Ettringer Bellerberg, Eifel, Deutschland

Zusammenfassung Das neue Mineral Ternesit, Ca₅(SiO₄)₂SO₄, wurde am Ettringer Bellerberg bei Mayen, Eifel, Deutschland gefunden. Die schon vom synthetischen Analogen her bekannte Kristallstruktur wurde aus Einkristalldaten von natürlichem Material verfeinert: Das Mineral ist orthorhombisch, Raumgruppe Pnma mit a= 6.863(1)Å, b=15.387(2) Å, c=10.181(1) Å, Z=4, R=0.058, R_w=0.046 für 820 unabhängige Reflexe mit F₀> 3(F₀) und 96 variablen Parametern. Die stärksten Maxima im Pulverbeugungsdiagramm sind (d-Wert (Å),I, hkl): 2.830, 100, (033)/2.853, 63, (230)/2.565, 55, (060)/ 3.198, 42, (132)/1.892, 39, (035) + (125). Das Mineral ist optisch zweiachsig negativ mit Brechungsindizes n_x = 1.630(1) (parallel [100]), n_y = 1.637 (2) (parallel [001]), und n_z = 1.640(1) (parallel [010]). Der optische Achsenwinkel 2V_x wurde zu 63.5(5)° gemessen.

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With 1 figure     

Phase transition in K2Cd2(SO4)3: Order parameter and microscopic distortions

The transition from P2₁3(T ⁴) to P2₁2₁2₁(D ₂ ⁴ ) in the langbeinite K₂Cd₂(SO₄)₃ has been analyzed using group theoretical methods and previously published structural data above and below the transition. We find that because the transition is strongly first-order, the primary-order parameter has relatively large values at the transition temperature, and higher order terms which involve the order parameter, the strain, and the coupling of the two must be included in the Landau expansion for the free energy. Complex displacements occur at the transition for all atoms of the unit cell, but these displacements can be resolved into contributions which can be shown from symmetry considerations to transform as the _{2 3} irrep of P2 ₁ 3(T ⁴) as well as contributions from symmetry-preserving displacements which transform under the irrep ₁. Therefore, the transition is not a simple one and involves sulfate rotations and cadmium and potassium ion displacements.     

高温高压下石膏脱水相变的原位拉曼光谱研究

本文运用激光拉曼光谱仪,利用水热金刚石压腔装置对高温高压条件下石膏-水体系中的石膏脱水相变进行拉曼光谱研究.在压力0.1 MPa～837.9 MPa和温度16～200 ℃条件下通过系列实验对相变的过程进行了原位光谱分析.与人们已知的无水条件下石膏分两步脱水的过程不同,高压下石膏在饱和水环境下倾向于一次性的脱去所有结晶水而形成无水石膏,实验中没有观察到半水石膏的出现.通过实验数据得到石膏和无水石膏的转折温度和平衡压力间的关系式为P(MPa)=19.56·T(℃)-2926.5.     

Phase transitions in langbeinites II: Raman spectroscopic investigations of K2Cd2(SO4)3

Polarized single crystal Raman spectra of the langbeinite K₂Cd₂(SO₄)₃ were recorded for different polarisations. With a view to understanding the phase transition mechanism, the lattice vibrational spectra (0–300 cm^?1), as well as the SO₄ symmetric stretching mode v ₁ (1,022 cm^?1), were recorded at different temperatures. No soft modes were observed. From the study of the temperature variation of the integrated intensity I ₀ and band width Γ of the hard mode (1,022 cm^?1), both SO₄ libration and SO₄ order/disorder models were ruled out as possible phase transition models. On the other hand, the model of Speer and Salje (paper I), involving the distortion of the polyhedra around Cd and K ions, explains the observed temperature behaviour of the Raman spectra very well. The consequences of a possible hypothetical high-temperature phase are discussed.     

First investigations on the quaternary system Na2O-K2O-CaO-SiO2: synthesis and crystal structure of the mixed alkali calcium silicate K1.08Na0.92Ca6Si4O15

Mineralogy and Petrology - In the course of an exploratory study on the quaternary system Na2O-K2O-CaO-SiO2 single crystals of the first anhydrous sodium potassium calcium silicate have been...     

Phase transition of potassium sulfate,K2SO4 (III); thermodynamical and phenomenological study

The orthorhombic-hexagonal phase transition of K₂SO₄ has been investigated by measurements of the temperature dependencies of the specific heat, expansion, and X-ray intensity of superstructure reflections, correlated with the structural point of view. The values of the net enthalpy and entropy changes are ΔH=4.28 KJ/mol and ΔS=4.98 J/mol·K at the phase transition temperature (587°C), respectively. The thermal expansion along the c axis shows strong anisotropic character above about 300°C and exhibits a very large discontinuous increase at 587°C, whereas those along the a and b axes increase linearly and exhibit small discontinuous decreases at 587°C. The X-ray intensity of superstructure reflections in the low-temperature form gradually decrease with increasing temperature, and come to extinction at 587°C, exhibiting a discontinuity. The observed entropy change and pressure dependence of the phase transition temperature were explained successfully by the use of results of the structural analysis and measured physical properties. The temperature dependencies of the spontaneous strain, X-ray intensity of superstructure reflection, and birefringence were consistently described by introducing a transition parameter on the basis of an instability at the M point in the Brillouin zone of the hexagonal phase.     

Diffusion and the dynamics of displacive phase transitions in cryolite (Na3AlF6) and chiolite (Na5Al3F14): Multi-nuclear NMR studies

Cryolite is a mixed-cation perovskite (Na₂(NaAl)F₆) which undergoes a monoclinic to orthorhombic displacive phase transition at ～550° C. Chiolite (Na₅Al₃F₁₄) is associated with cryolite in natural deposits, and consists of sheets of corner sharing [AlF₆] octahedra interlayered with edge-sharing [NaF₆] octahedra. Multi-nuclear NMR line shape and relaxation time (T₁) studies were performed on cryolite and chiolite in order to gain a better understanding of the atomic motions associated with the phase transition in cryolite, and Na diffusion in cryolite and chiolite. ²⁷Al, ²³Na, and ¹⁹F static NMR spectra and T₁'s in cryolite suggest that oscillatory motions of the [AlF₆] octahedra among four micro-twin and anti-phase domains in α-cryolite begin at least 150° C below the transition temperature and persist above it. Variable temperature ²³Na MAS NMR further indicates diffusional exchange at a rate of at least 13 kHz between the Na sites by the time the transition temperature is reached. ²⁷Al and ²³Na T₁'s show the same behavior with increasing temperature, indicating the same relaxation mechanisms are responsible for both. The first order nature of the cryolite transition is apparent as a jump in the ²³Na and ²⁷Al T₁'s. Above the transition temperature, the T₁'s decrease slightly indicating that the motions responsible for the drop in T₁, are still present above the transition, further supporting the dynamic nature of the high temperature phase of cryolite. Chiolite ²³Na static spectra decrease in linewidth with increasing temperature, indicating increased Na diffusion, which is interpreted as occurring within the [NaF₆] sheets in the chiolite structure, but not between the two different Na sites. ²⁷Al and ²³Na T₁'s show similar behavior as in cryolite, but there is no discontinuity due to a phase transition. ¹⁹F T₁'s are constant from room temperature to 150° C indicating no oscillatory motion of the [AlF₆] octahedra in chiolite.     

Investigation of phase relations in the (Na,K)AlGeO4 system

The phase relations in the (Na,K)AlGeO₄ system have been investigated at atmospheric pressure over the temperature range 700–1100° C by X-ray powder diffraction and electron diffraction/microscopy. Four distinct structure-types occur in this system including the beryllonite, nepheline, kalsilite and KAlGeO₄ types in order of increasing KAlGeO₄ content. In contrast to the (Na,K)Al-SiO₄ system, the nepheline structure is only stable over a narrow composition range around 25 percent K at temperatures above approximately 800° C and transforms reconstructively into the beryllonite structure at lower temperatures. The formation of domain microstructures in some K-rich phases has been directly observed by high-resolution electron microscopy and can be associated with the presence of diffuse scattering in their diffraction patterns. The structural trend observed across the (Na,K)AlGeO₄ series as a function of composition can be rationalized to a large extent in terms of the dependence of the framework topology of these tridymite-derivative structures on the size of the alkali atoms.