High temperature and composition induced phase transitions in LiZnV1-xAsxO4 phenacites: Crystal structure and Raman spectroscopy studies.

In this work, using techniques of X-ray diffraction and Raman spectroscopy, we report the composition and high-temperature induced phase transition in the system LiZnV1-xAsxO4 (0⩽x⩽1). Both techniques showed that the increase of arsenic amount induced a structural transition from R-3 LiZnVO4 type to LiZnAsO4 type belonging to R3 space group, the transition occurring between x=0.7 and x=0.8. Furthermore, increasing temperature for the compositions (0.8⩽x⩽1) manifests a transition from the LiZnAsO4 structural type with R3 space group to the R-3 LiZnVO4 structural type. For this series, the transition from the space group R3 to the centro-symmetric space group R-3 shows considerable changes in the compositional and temperature dependencies of the bands: spectral positions of all the observed Raman bands exhibit shifts linearly proportional to the temperature increase, with points of shift-rate changes revealing a symmetry change. The Raman-spectra based temperature-composition phase diagram confirms the results obtained using the method of Rietveld refinements, thus showing the R-3 to R3 transition occurring between x=0.7 and 0.8.

Elaboration, Rietveld refinements and vibrational spectroscopic study of Na1-xKxCaPb3(PO4)3 lacunar apatites (0 ⩽ x ⩽ 1).

Synthesis of apatites, Na1-xKxCaPb3(PO4)3 0 ⩽ x ⩽ 1, with anion vacancy were carried out using solid state reactions. The solid solution of apatite-type structure crystallize in the hexagonal system, space group P63/m (No. 176). Rietveld refinements showed that around 90% of Pb(2+) cations are located in the (6h) sites, the left amount of Pb(2+) cations are located in the (4f) sites; 27-31% of Ca(2+) cations are located in the (6h) sites, the left amount of Ca(2+) cations are located in the (4f) sites. The ninefold coordination sites (4f) are also occupied by the K(+) and Na(+) monovalent ions. The structure can be described as built up from [PO4](3-) tetrahedra and Pb(2+)/Ca(2+) of sixfold coordination cavities (6h positions), which delimit void hexagonal tunnels running along [001]. These tunnels are connected by cations of mixed sites (4f) which are half occupied by Pb(2+)/Ca(2+) and half by Na(+)/K(+) mixed cations. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit cell group analysis and by comparison with other apatites. Vibrational spectra of all the compositions are similar and show some linear shifts of the frequencies as a function of the composition toward lower values due the substitutions of Na(+) by K(+) with a larger radius.

Vibrational spectra and factor group analysis of M0.50TiOPO4 oxyphosphates (M=Mg, Zn, Ni, Co, Fe and Cu).

Raman spectra of a series of orthophosphates M(0.50)TiO(PO(4)) (M=Mg, Zn, Ni, Co, Fe, and Cu) have been recorded in crystalline state. Factor group analysis has been performed for space group P2(1)/c and assignments of the internal modes of the [PO(4)] tetrahedra and [TiO(6)] octahedra have been made.

Stability of Perovskite (MgSiO3) in the Earth's Mantle

Available thermodynamic data and seismic models favor perovskite (MgSiO3) as the stable phase in the mantle. MgSiO3 was heated at temperatures from 1900 to 3200 kelvin with a Nd-YAG laser in diamond-anvil cells to study the phase relations at pressures from 45 to 100 gigapascals. The quenched products were studied with synchrotron x-ray radiation. The results show that MgSiO3 broke down to a mixture of MgO (periclase) and SiO2 (stishovite or an unquenchable polymorph) at pressures from 58 to 85 gigapascals. These results imply that perovskite may not be stable in the lower mantle and that it might be necessary to reconsider the compositional and density models of the mantle.

Discussion comment on melting criteria and imaging spectroradiometry in laser-heated diamond-cell experiments (by R. Jeanloz & A. Kavner).

Jeanloz & Kavner have a very timely contribution which raises some very important issues concerning the measurement of temperature using spectroradiometry. In this discussion of the paper, we intend to show that while all the issues raised by the authors should be of real concern to all workers, some of the issues have indeed been resolved with improved technique. However, we agree with the authorn that there are several issues that must be resolved and caution is necessary in interpreting the observations.

Temperatures in Earth's Core Based on Melting and Phase Transformation Experiments on Iron.

Experiments on melting and phase transformations on iron in a laser-heated, diamond-anvil cell to a pressure of 150 gigapascals (approximately 1.5 million atmospheres) show that iron melts at the central core pressure of 363.85 gigapascals at 6350 +/- 350 kelvin. The central core temperature corresponding to the upper temperature of iron melting is 6150 kelvin. The pressure dependence of iron melting temperature is such that a simple model can be used to explain the inner solid core and the outer liquid core. The inner core is nearly isothermal (6150 kelvin at the center to 6130 kelvin at the inner core-outer core boundary), is made of hexagonal closest-packed iron, and is about 1 percent solid (MgSiO(3) + MgO). By the inclusion of less than 2 percent of solid impurities with iron, the outer core densities along a thermal gradient (6130 kelvin at the base of the outer core and 4000 kelvin at the top) can be matched with the average seismic densities of the core.

Experimental Evidence for a New Iron Phase and Implications for Earth's Core.

Iron is known to occur in four different crystal structural forms. One of these, the densest form (epsilon phase, hexagonal close-packed) is considered to have formed Earth's core. Theoretical arguments based on available high-temperature and high-pressure iron data indicate the possibility of a fifth less dense iron phase forming the core. Study of iron phase transition conducted between pressures of 20 to 100 gigapascals and 1000 to 2200 Kelvin provides an experimental confirmation of the existence of this new phase. Thee epsilon iron phase transforms to this lower density phase before melting. The new phase may form a large part of Earth's core.