High-pressure X-ray diffraction study of ε-FeOOH

An in situ synchrotron X-ray diffraction study was carried out on ε-FeOOH at room temperature up to a pressure of 8.6 GPa using the energy-dispersive method. The linear compressibility was determined to be β _a  = 1.69(3) × 10⁻³ GPa⁻¹, β _b  = 2.86(6) × 10⁻³ GPa⁻¹, and β _c  = 1.73(5) × 10⁻³ GPa⁻¹. The b-axis of the unit cell is more compressible than the a and c axes. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state. The best fit was found using a room temperature isothermal bulk modulus of K ₀ = 126(3) GPa and its pressure derivative K′ = 10(1).     

High-temperature behaviour of melilite: in situ X-ray diffraction study of gehlenite–åkermanite–Na melilite solid solution

High-temperature X-ray diffraction experiments have been performed on melilite solid solutions, on single crystal and powder samples. In åkermanite–gehlenite series, the volumetric thermal expansion increases from gehlenite, 26.5(2) E-06 K-1, to åkermanite, 31.2(1) E-06 K-1. The variation is related to the cation content in the tetrahedral T1 site of the structure, and the linear expansion along the a axis has the greatest variation as a function of composition. The expansion perpendicular to the tetrahedral layers does not present any significant variation as a function of composition. In the åkermanite–Na melilite series, the presence of Na in the [8]-coordinated site strongly increases the linear expansion along the c axis, while the volumetric expansion decreases from åkermanite to Na melilite, whose value can be extrapolated to 27.4 E-06 K-1     

High-pressure single-crystal X-ray diffraction and synchrotron Mössbauer study of monoclinic ferrosilite

The phase and spin transitions in single-crystal monoclinic ferrosilite, FeSiO₃, were investigated using X-ray diffraction and Mössbauer spectroscopy up to lower-mantle pressures and room temperature in a helium pressure medium. Using single-crystal X-ray diffraction, we measured the equation of state of ferrosilite up to about 43 GPa. We observed a P2₁/c-to-C2/c phase transition between 1.5 and 1.7 GPa and a phase transition from C2/c to a distinct P2₁/c structure between 30 and 34 GPa. With time-domain Mössbauer spectroscopy, we determined the hyperfine parameters of ferrous iron up to 95 GPa. The phase transitions were correlated with discontinuities in Mössbauer spectral features. We observed the onset of high-spin-to-low-spin transitions in the M1 and M2 sites at ～37 GPa and ～74 GPa, respectively. Understanding the electronic structure of iron in a well-characterized single crystal of ferrosilite may help interpret the behavior of iron in complex dense silicate phases.     

Equation of state of adamite up to 11 GPa: a synchrotron X-ray diffraction study

The compression behavior of natural adamite [Zn₂AsO₄OH] has been investigated up to 11.07 GPa at room temperature utilizing in situ angle-dispersive X-ray diffraction and a diamond anvil cell. No phase transition has been observed within the pressure range investigated. A third-order Birch–Murnaghan equation of state fitted to all of the data points yielded V ₀ = 430.1(4) Å³, K ₀ = 80(3) GPa, K′ ₀ = 1.9(5). The K ₀ was obtained as 69(1) GPa when K′ ₀ was fixed at 4. Analysis of axial compressible moduli shows the intense compression anisotropy of adamite: K _a0 = 37(3) GPa, K _b0 = 153(6) GPa, K _c0 = 168(8) GPa; hence, a axis is the most compressible and the compressibility of b and c axis is comparable. Furthermore, the comparisons among the compressional properties of adamite, libethenite (Cu₂PO₄OH, also belongs to olivenite group), and andalusite (Al₂SiO₄O has the similar structure with adamite) at high pressure were made.     

Order–disorder–reorder process in thermally treated dolomite samples: a combined powder and single-crystal X-ray diffraction study

A combined powder and single-crystal X-ray diffraction analysis of dolomite [CaMg(CO₃)₂] heated to 1,200°C at 3 GPa was made to study the order–disorder–reorder process. The order/disorder transition is inferred to start below 1,100°C, and complete disorder is attained at approximately 1,200°C. Twinned crystals characterized by high internal order were found in samples annealed over 1,100°C, and their fraction was found to increase with temperature. Evidences of twinning domains combined with probable remaining disordered portions of the structure imply that reordering processes occur during the quench. Twin domains are hereby proposed as a witness to thermally induced intra-layer-type cation disordering.     

Single-crystal X-ray diffraction and spectroscopic studies on humboldtine and lindbergite: weak Jahn–Teller effect of Fe<Superscript>2+</Superscript> ion

The single-crystal of humboldtine [Fe²⁺(C₂O₄) · 2H₂O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)?, V = 518.0 (8) Å³, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C₂O₄)^2?] and Fe²⁺ ions forms one-dimensional chain structure parallel to [010]; water molecules (H₂O)⁰ create hydrogen bonds to link the chains, where (H₂O)⁰ is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe²⁺ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn²⁺(C₂O₄) · 2H₂O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe²⁺–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe²⁺ ion. These interpretations were also discussed in terms of bond-valence theory.     

X-ray photoelectron study of oxygen bonding in crystalline C–S–H phases

We recorded the photoelectron spectra of various crystalline calcium silicate hydrates (C–S–Hs) and have examined their O 1 s photoelectron spectra. The spectra are asymmetric, with contributions assigned primarily to bridging and non-bridging oxygen species. There is an increased contribution due to the presence of non-bonding oxygen atoms with increasing calcium:silicon ratio. Additionally, there are slight changes in theO 1s-binding energies with changes in calcium:silicon ratio. These changes are explained in terms of bonding and silicate structure.     

Thermal expansion of kyanite at ambient pressure: An X-ray powder diffraction study up to 1000 ℃

The thermal expansion coefficients of kyanite at ambient pressure have been investigated by an X-ray powder diffraction technique with temperatures up to 1000 ℃. No phase transition was observed in the experimental temperature range. Data for the unit-cell parameters and temperatures were fitted empirically resulting in the following thermal expansion coefficients: aa = 5.8(3) × 10-5, ab = 5.8 (1) × 10-5, ac% = 5.2(1) × 10-5, and av = 7.4(1) × 10-3 ℃-1, in good agreement with a recent neutron powder diffraction study. On the other hand, the variation of the unit-cell angles a, β and γ of kyanite with increase in temperature is very complicated, and the agreement among all studies is poor. The thermal expansion data at ambient pressure reported here and the compression data at ambient temperature from the literature suggest that, for the kyanite lattice, the most and least thermally expandable directions correspond to the most and least compressible directions, respectively.     

Thermal expansion of kyanite at ambient pressure： An X-ray powder diffraction study up to 1000 ℃

The thermal expansion coefficients of kyanite at ambient pressure have been investigated by an X-ray powder diffraction technique with temperatures up to 1000 °C. No phase transition was observed in the experimental temperature range. Data for the unit-cell parameters and temperatures were fitted empirically resulting in the following thermal expansion coefficients: αa = 5.8(3) × 10?5, αb = 5.8(1) × 10?5, αc = 5.2(1) × 10?5, and αV = 7.4(1) × 10?3 °C?1, in good agreement with a recent neutron powder diffraction study. On the other hand, the variation of the unit-cell angles α, β and γ of kyanite with increase in temperature is very complicated, and the agreement among all studies is poor. The thermal expansion data at ambient pressure reported here and the compression data at ambient temperature from the literature suggest that, for the kyanite lattice, the most and least thermally expandable directions correspond to the most and least compressible directions, respectively.     

Neutron diffraction study of aluminous hydroxide δ-AlOOD

We have determined the position of deuterium atoms in δ-AlOOD by neutron powder diffraction at ambient pressure. As previously reported by theoretical and experimental studies, the deuterium atoms are located in the tunnel formed by the chains of AlO₆ octahedra. The data are best fit with the P2₁ nm structure, producing bond lengths of D–O1 of 1.552(2) Å, O2–D of 1.020(2) Å and O1–O2 of 2.571(2). This study confirms that the hydrogen bond is asymmetric at ambient conditions in agreement with recent single-crystal synchrotron study for δ-AlOOH.     

Study of pocyclic aromatic hydrocarbons at a pressure of 6–9 GPa with X-ray diffraction and synchrotron radiation

This work is one of the stages of study of the deep C-O-H fluid and investigates the behavior of polycyclic aromatic hydrocarbons (PAHs) under conditions of the Earth’s mantle. The composition of the C-O-H fluid in the upper mantle is estimated as a mixture of H₂O and CH₄ with a minor amount of H₂ and heavier hydrocarbons. Some theoretical calculations show that the stability of heavy hydrocarbons (alkanes, alkenes, and PAHs) increases with an increase in temperature. This paper presents the results of an XRD study of PAHs stability in multianvil presses on a Spring-8 accelerator (Japan). The primary compositions were chosen according to the abundance of PAHs in nature. In situ diffraction spectrums were recorded to determine the PAHs stability field. It was established that the PAHs become unstable at a pressure of 6–9 GPa and a temperature of 873–1073 K.     

Observation of pressure-induced phase transition of δ-AlOOH by using single-crystal synchrotron X-ray diffraction method

Pressure-induced phase transition of δ-AlOOH was confirmed between 6.1 and 8.2 GPa by using a single-crystal synchrotron X-ray diffraction method. The phase transition is reversible and unquenchable. Results from analysis of the distribution of X-ray diffraction intensities at 8.2 GPa reveal an additional systematic, absence of k + l odd for 0kl in comparison with h + l odd for h0l observed prior to the phase transition (space group, P2₁ nm). The space group of the post-transition phase should be Pnnm or Pnn2 to satisfy the systematic absence rule. Crystal structure refinements of the post-transition phase conducted for the three models (Pnnm, Pnn2, and P2₁ nm) indicate that the space group of the post-transition phase is Pnnm. The O–O distance of hydrogen bond in the post-transition phase at 8.2 GPa is 2.439(6) Å and is significantly longer than the predicted distance (2.366 Å) of the hydrogen bond symmetrization in δ-AlOOH. The H distribution in the post-transition phase would display a fully disordered hydrogen bond pattern.     

High-pressure elastic behavior of Ca4La6(SiO4)6(OH)2 a synthetic rare-earth silicate apatite: a powder X-ray diffraction study up to 9.33 GPa

The compression behavior of a synthetic Ca₄La₆(SiO₄)₆(OH)₂ has been investigated to about 9.33 GPa at 300 K using in situ angle-dispersive X-ray diffraction and a diamond anvil cell. No phase transition has been observed within the pressure range investigated. The values of zero-pressure volume V ₀, K ₀, and $K_{0}^{'}$ refined with a third-order Birch–Murnaghan equation of state are V ₀ = 579.2 ± 0.1 Å³, K ₀ = 89 ± 2 GPa, and $K_{0}^{'} = 10.9 \pm 0.8$ . If $K_{0}^{'}$ is fixed at 4, K ₀ is obtained as 110 ± 2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a0 = 79 ± 2 GPa) is more compressible than the c-axis (K _c0 = 121 ± 7 GPa). A comparison between the high-pressure elastic response of Ca₄La₆(SiO₄)₆(OH)₂ and the iso-structural calcium apatites is made. The possible reasons of the different elastic behavior between Ca₄La₆(SiO₄)₆(OH)₂ and calcium apatites are discussed.     

High-pressure neutron diffraction study on H–D isotope effects in brucite

A neutron powder diffraction study of hydrogenated and deuterated brucite was conducted at ambient temperature and at pressures up to 9 GPa, using a Paris–Edinburgh high-pressure cell at the WAND instrument of the ORNL High Flux Isotope Reactor. The two materials were synthesized by the same method and companion measurements of neutron diffraction were conducted under the same conditions. Our refinement results show that the lattice-parameters of the a axis, parallel to the sheets of Mg–O octahedra, decrease only slightly with pressure with no effect of H–D substitution. However, the c axis of Mg(OD)₂ is shorter and may exhibit greater compressibility with pressure than that of Mg(OH)₂. Consequently, the unit-cell volume of deuterated brucite is slightly, but systematically smaller than that of hydrogenated brucite. When fitted to a third-order Birch–Murnaghan equation in terms of the normalized unit-cell volume, values of the bulk modulus for hydrogenated and deuterated brucite (K ₀ = 39.0 ± 2.8 and 40.4 ± 1.3 GPa, respectively) are, however, indistinguishable from each other within the experimental errors. The measured effect of H–D substitution on the unit-cell volume also demonstrates that brucite (and other hydrous minerals) preferentially incorporate deuterium over hydrogen under pressure, suggesting that the distribution of hydrogen isotopes in deep-earth conditions may differ significantly from that in near-surface environments.     

The strength of ruby from X-ray diffraction under non-hydrostatic compression to 68 GPa

Polycrystalline ruby (α-Al₂O₃:Cr³⁺), a widely used pressure calibrant in high-pressure experiments, was compressed to 68.1 GPa at room temperature under non-hydrostatic conditions in a diamond anvil cell. Angle-dispersive X-ray diffraction experiments in a radial geometry were conducted at beamline X17C of the National Synchrotron Light Source. The stress state of ruby at high pressure and room temperature was analyzed based on the measured lattice strain. The differential stress of ruby increases with pressure from ~3.4 % of the shear modulus at 18.5 GPa to ~6.5 % at 68.1 GPa. The polycrystalline ruby sample can support a maximum differential stress of ~16 GPa at 68.1 GPa under non-hydrostatic compression. The results of this study provide a better understanding of the mechanical properties of this important material for high-pressure science. From a synthesis of existing data for strong ceramic materials, we find that the high-pressure yield strength correlates well with the ambient pressure Vickers hardness.     

Structural evolution of a 2M 1 phengite mica up to 11 GPa: an in situ single-crystal X-ray diffraction study

The structural evolution at high pressure of a natural 2M ₁-phengite [(K_0.98Na_0.02)_Σ=1.00(Al_1.55Mg_0.24Fe_0.21Ti_0.02)_Σ=2.01(Si_3.38Al_0.62)O₁₀(OH)₂; a = 5.228(2), b = 9.057(3), c = 19.971(6)Å, β = 95.76(2)°; space group: C2/c] from the metamorphic complex of Cima Pal (Sesia Zone, Western Alps, Italy) was studied by single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions up to ~11 GPa. A series of 12 structure refinements were performed at selected pressures within the P range investigated. The compressional behaviour of the same phengite sample was previously studied up to ~25 GPa by synchrotron X-ray powder diffraction, showing an irreversible transformation with a drastic decrease of the crystallinity at P > 15–17 GPa. The elastic behaviour between 0.0001 and 17 GPa was modelled by a third-order Birch–Murnaghan Equation of State (BM-EoS), yielding to K _T0 = 57.3(10) GPa and K′ = ?K _T0/?P = 6.97(24). The single-crystal structure refinements showed that the significant elastic anisotropy of the 2M ₁-phengite (with β(a):β(b):β(c) = 1:1.17:4.60) is mainly controlled by the anisotropic compression of the K-polyhedra. The evolution of the volume of the inter-layer K-polyhedron as a function of P shows a negative slope, Fitting the P–V(K-polyhedron) data with a truncated second-order BM-EoS we obtain a bulk modulus value of K _T0(K-polyhedron) = 26(1) GPa. Tetrahedra and octahedra are significantly stiffer than the K-polyhedron. Tetrahedra behave as quasi-rigid units within the P range investigated. In contrast, a monotonic decrease is observed for the octahedron volume, with K _T0 = 120(10) GPa derived by a BM-EoS. The anisotropic response to pressure of the K-polyhedron affects the P-induced deformation mechanism on the tetrahedral sheet, consisting in a cooperative rotation of the tetrahedra and producing a significant ditrigonalization of the six-membered rings. The volume of the K-polyhedron and the value of the ditrigonal rotation parameter (α) show a high negative correlation (about 93%), though a slight discontinuity is observed at P >8 GPa. α increases linearly with P up to 7–8 GPa (with ?α/?P ≈ 0.7°/GPa), whereas at higher Ps a “saturation plateau” is visible. A comparison between the main deformation mechanisms as a function of pressure observed in 2M ₁- and 3T-phengite is discussed.