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Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressuretemperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-III, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment. [ABSTRACT FROM AUTHOR]

Lattice strength and structural phase transitions of gadolinium (Gd) were determined under nonhydrostatic compression up to 55 GPa using an angle-dispersive radial x-ray diffraction technique in a diamond-anvil cell at room temperature. Three new phases of fcc structure, dfcc structure, and new monoclinic structure were observed at 25 GPa, 34 GPa, and 53 GPa, respectively. The radial x-ray diffraction data yield a bulk modulus K0=36(1) GPa with its pressure derivate K0'=3.8(1) at the azimuthal angle between the diamond cell loading axis and the diffraction plane normal and diffraction plane ψ=54.7°. With K0' fixed at 4, the derived K0 is 34(1) GPa. In addition, analysis of diffraction data with lattice strain theory indicates that the ratio of differential stress to shear modulus (t/G) ranges from 0.011 to 0.014 at pressures of 12-55 GPa. Together with estimated high-pressure shear moduli, our results show that Gd can support a maximum differential stress of 0.41 GPa, while it starts to yield to plastic deformation at 16 GPa under uniaxial compression. The yield strength of Gd remains approximately a constant with increasing pressure, and reaches 0.46 GPa at 55 GPa. [ABSTRACT FROM AUTHOR]

The melting curve of H2O has been measured by in situ Raman spectroscopy in an externally heated diamond anvil cell up to 22 GPa and 900 K. The Raman-active OH-stretching bands and the translational modes of H2O as well as optical observations are used to directly and reliably detect melting in ice VII. The observed melting temperatures are higher than previously reported x-ray measurements and significantly lower than recent laser-heating determinations. However, our results are in accord with earlier optical determinations. The frequencies and intensities of the OH-stretching peaks change significantly across the melting line while the translational mode disappears altogether in the liquid phase. The observed OH-stretching bands of liquid water at high pressure are very similar to those obtained in shock-wave Raman measurements. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In situ high P-T Raman spectra of solid CO2 up to 67 GPa and 1660 K have been measured, using a micro-optical spectroscopy system coupled with a Nd:YLF laser heating system in diamond anvil cells. A metallic foil was employed to efficiently absorb the incoming Nd:YLF laser and heat the sample. The average sample temperature was accurately determined by detailed balance from the anti-Stokes/Stokes ratio, and was compared to the temperature of the absorber determined by fitting the thermal radiation spectrum to the Planck radiation law. The transformation temperature threshold and the transformation dynamics from the molecular phases III and II to the polymeric phase V, previously investigated only by means of temperature quench experiments, was determined at different pressures. The P-T range of the transformation, between 640 and 1100 K in the 33–65 GPa pressure interval, was assessed to be a kinetic barrier rather than a phase boundary. These findings lead to a new interpretation of the high P-T phase diagram of carbon dioxide. Furthermore, our approach opens a new way to perform quantitative in situ Raman measurements under extremely high pressures and temperatures, providing unique information about phase relations and structural and thermodynamic properties of materials under these conditions. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We describe an in situ high pressure-temperature Raman technique for studying materials in laser-heated diamond anvil cells using a Nd:YLF laser (1053 nm) as the heating source and an ion laser as the Raman exciting source. Here we introduce the method of laser heating transparent samples using a metallic foil (Pt,Re, or W) as the laser absorber (internal heating furnace) in a diamond cell. The YLF laser is used to effectively laser-heat one side of a metal foil 5–15 μm thick with a small hole of 10–20 μm in diameter at the center. The foil, in turn, heats a transparent sample while the Raman signals excited by an Ar+ or Kr+ laser are measured. Temperature of the laser-heated foil is measured by means of spectroradiometry whereas the average temperature of the heated sample is independently determined from the intensity ratios of the anti-Stokes/Stokes excitation pairs. The intrinsic temperature-dependent asymmetry of the Raman spectra arises from the principle of the detailed balance and is independent of sample properties other than the temperatures. The average determined by the signal-to-noise ratio of anti-Stokes/Stokes excitation pairs gives the sample temperature with the statistical accuracy of the Raman spectra. Transparent samples such as CO2 have been heated up to 1600 K and 65 GPa and Raman spectra have been measured with temperature uncertainty of 50–100 K. In situ Raman spectroscopy by laser heating represents a powerful technique to characterize high pressure-temperature properties of materials including molecular systems present in planetary interiors. [ABSTRACT FROM AUTHOR]