Synchrotron X-ray powder diffraction and infrared (IR) spectroscopy studies on natural brucite were conducted up to 31 GPa using diamond-anvil cell (DAC) techniques at beamlines X17C and U2A of National Synchrotron Light Source (NSLS). The lattice parameters and unit-cell volumes were refined in P3m1 space group throughout the experimental pressure range. The anisotropy of lattice compression decreases with pressure due to a more compressible c axis and the compression becomes nearly isotropic in the pressure range of 10-25 GPa. The unit-cell volumes are fitted to the third-order Birch-Murnaghan equation of state, yielding K 0 = 39.4(1.3) GPa, K 0 ′ = 8.4(0.4) for the bulk modulus and its pressure-derivative, respectively. No phase transition or amorphization was resolved from the X-ray diffraction data up to 29 GPa, however, starting from ~4 GPa, a new infrared vibration band (~3638 cm -1 ) 60 cm -1 below the OH stretching A 2u band of brucite was found to coexist with the A 2u band and its intensity continuously increases with pressure. The new OH stretching band has a more pronounced redshift as a function of pressure (-4.7 cm -1 /GPa) than the A 2u band (-0.7 cm -1 / GPa). Comparison with first-principles calculations suggests that a structural change involving the disordered H sublattice is capable of reconciling the observations from X-ray diffraction and infrared spectroscopy studies.

No abstract

A simple external heating assemblage allowing diamond anvil cell experiments at pressures up to 34 GPa and temperatures up to 653 K was constructed. This cell can be connected to the synchrotron radiation conveniently. The design and construction of this cell are fully described, as well as its applications for x-ray diffraction. Heating is carried out by using an external-heating system, which is made of NiCr resistance wire, and the temperature was measured by a NiCr-NiSi or PtRh-Pt thermocouple. We showed the performance of the new system by introducing the phase transition study of cinnabar (alpha-HgS) and thermal equation of state study of almandine at high pressure and temperature with this cell.

Crystal-chemical properties of synthetic Almandine-Pyrope (Alm-Pyr) solid solutions were investigated by X-ray single-crystal diffraction and Raman spectroscopy. Garnet solid solution with different compositions were synthesized from powder at 4.0 GPa and annealed at 1200 °C for 48 h by a multi-anvil pressure apparatus. Garnet crystals with different sizes (about 60-1000 μm) were obtained from synthesis. The results of X-ray single-crystal diffraction show that the unit cell constants decrease with increasing Pyr contents in the synthetic Alm-Pyr crystals due to the smaller ionic radius of Mg2+ in eightfold coordination than that of Fe2+. The data exhibit obviously positive deviations from ideal mixing volumes across the Alm-Pyr join which may be caused by the distortion of the SiO4 tetrahedron. Moreover, the significant decrease in the average M-O bond length and volume of the [MgO8]/[FeO8] dodecahedron with increasing Pyr contents are the most important factors to the decrease in the Alm-Pyr crystal unit cell constant and volume. On the other hand, selected bond distances (average <M-O>, <Al-O>, and <D-O> distances) have a linear correlation with the unit-cell parameter, but the <Si-O> distance has nonlinear correlation. With increasing the unit-cell parameter, the average <M-O> distance increases significantly, followed by the average <D-O> and <Al-O> distances. While the <Si-O> distance changes negligibly further confirming the conclusion that the significant decrease of the average M-O bond length of the [MgO8]/[FeO8] dodecahedron with increasing Pyr contents are the most important factors to the decrease in the Alm-Pyr crystal unit cell volume. In the Raman spectra collected for the Alm-Pyr solid solutions, Raman vibration mode assignments indicate that the Raman vibrational spectra change along the Alm-Pyr binary solution. The mode frequencies of Si-O stretching, Si-O bending, and the rotation of the SiO4-tetrahedron (R(SiO4)) decrease linearly, while the translational modes of the SiO4-tetrahedron (T(SiO4)) increase with increasing Alm contents.