Crystal-liquid-vapor equilibrium experiments at high temperature (less than or equal to 1800 C) and low, controlled oxygen and hydrogen pressure (10(-1) to 10(-9) PA)

Evidence from carbonaceous chrondrites points to refractory oxides in the system CaO-MgO-Al2O3-TiO2-SiO2-Fe-O as being among the earliest phases to condense from the solar nebula. It is necessary to establish the equilibrium relationships between the relevant crystalline and amorphous phases before the chemical constraints can be meaningfully applied to models of solar system history. Preliminary experiments on earth show that such experiments are feasible. Earth-based experiments suffer from several unavoidable problems. These problems can be overcome by experimentation in the Space Station where the experiments can be conducted under near static pressure conditions and where total pressure equals the sum of controlled hydrogen and oxygen pressures and can be controlled for periods exceeding several hours

Improved modelling of liquid GeSe2_2: the impact of the exchange-correlation functional

The structural properties of liquid GeSe$_2$ are studied by using first-principles molecular dynamics in conjuncton with the Becke, Lee, Yang and Parr (BLYP) generalized gradient approximation for the exchange and correlation energy. The results on partial pair correlation functions, coordination numbers, bond angle distributions and partial structure factors are compared with available experimental data and with previous first-principle molecular dynamics results obtained within the Perdew and Wang (PW) generalized gradient approximation for the exchange and correlation energy. We found that the BLYP approach substantially improves upon the PW one in the case of the short-range properties. In particular, the Ge$-$Ge pair correlation function takes a more structured profile that includes a marked first peak due to homopolar bonds, a first maximum exhibiting a clear shoulder and a deep minimum, all these features being absent in the previous PW results. Overall, the amount of tetrahedral order is significantly increased, in spite of a larger number of Ge$-$Ge homopolar connections. Due to the smaller number of miscoordinations, diffusion coefficients obtained by the present BLYP calculation are smaller by at least one order of magnitude than in the PW case.Comment: 6 figure

Effects of water and fluorine on the viscosity of albite melt at high pressure: a preliminary investigation

The viscosities of fluorine- and water-bearing melts based on albite composition have been determined at 7.5, 15 and 22.5 kbar by the falling-sphere method. All melt viscosities decrease isothermally with increasing pressure. At 1200°C the viscosity of the fluorine-bearing melt (albite + 5.8 wt.% fluorine substituted for oxygen, denoted AbF2O−1) decreases from5000 ± 750P at7.5kbar to1600 ± 240P at22.5kbar. At 1400°C the viscosity of this melt decreases from1300 ± 200P at7.5kbar to430 ± 65P at22.5kbar. At 1400°C the viscosity of albite + 2.79 wt.% water (denoted AbH2O) decreases from650 ± 100P at7.5kbar to400 ± 60P at22.5kbar. Fluorine (as F2O−1) and water strongly decrease the viscosity of albite melt over the entire range of investigated pressures. The ratio of the effects of 5.8 wt.% fluorine [F/(F + O)molar = 0.10] and 2.79 wt.% water [OH/(OH + O)molar = 0.10] on the log of melt viscosity [Δ log η(AbF2O−1)/Δ log η(AbH2O)] equals0.90 ± 0.05, 0.84 ± 0.05and0.97 ± 0.05at7.5, 15and22.5kbar, respectively. Comparison with available data on the high-pressure viscosity of albite melt indicates that both F2O−1 and H2O maintain their viscosity-reducing roles to lower crustal pressures. The difference between the viscosities of melts of albite, AbF2O−1 and AbH2O, may be explained in terms of the relatively depolymerized structures of AbF2O−1 and AbH2O melts. The depolymerization of albite melt by the addition of water results from the formation of SiOH bonds. The depolymerization of albite melt by F2O−1 substitution results from the formation of non-bridging oxygens associated with network-modifying aluminum cations that are formed upon fluorine solution. The strong viscosity-reducing effects of water and fluorine in albite melt at pressures corresponding to the mid- to lower continental crust indicate that these two components will strongly influence the dynamic behavior of anatectic melts during initial magma coalescence and restite-melt segregation

Coreless Terrestrial Exoplanets

Differentiation in terrestrial planets is expected to include the formation of a metallic iron core. We predict the existence of terrestrial planets that have differentiated but have no metallic core--planets that are effectively a giant silicate mantle. We discuss two paths to forming a coreless terrestrial planet, whereby the oxidation state during planetary accretion and solidification will determine the size or existence of any metallic core. Under this hypothesis, any metallic iron in the bulk accreting material is oxidized by water, binding the iron in the form of iron oxide into the silicate minerals of the planetary mantle. The existence of such silicate planets has consequences for interpreting the compositions and interior density structures of exoplanets based on their mass and radius measurements.Comment: ApJ, in press. 22 pages, 5 figure

Rigidity and intermediate phases in glasses driven by speciation

The rigid to floppy transitions and the associated intermediate phase in glasses are studied in the case where the local structure is not fully determined from the macroscopic concentration. The approach uses size increasing cluster approximations and constraint counting algorithms. It is shown that the location and the width of the intermediate phase and the corresponding structural, mechanical and energetical properties of the network depend crucially on the way local structures are selected at a given concentration. The broadening of the intermediate phase is obtained for networks combining a large amount of flexible local structural units and a high rate of medium range order.Comment: 4 pages, 4 figure

The effect of temperature and bulk composition on the solution mechanism of phosphorus in peraluminous haplogranitic magma.

Solution mechanisms of P in peraluminous glasses and melts in the system CaO-Na2O-K2O-Al2O3- SiO2-P2O5 have been examined with in-situ microRaman spectroscopy from ambient temperature to near 1200 °C. The principal aim was to examine the relative stabilities of phosphate complexes as functions of P content, peraluminosity, and temperature. Increasing peraluminosity was accomplished by increasing the proportions of Al3+ and Ca2+ of constant SiO2 content. The molar ratio Al2O3/ (CaO+Na2O+K2O) (A/CNK) ranged from ~1 to ~1.3. In all compositions, P5+ is bonded to Al3+ to form AlPO4 complexes. In addition, there is evidence for pyrophosphate complexing (P2O7). In melts with the highest (Ca+Na+K)/P, there is probably also a small fraction of orthophosphate complexes present. The relative importance of AlPO4-like complexes is correlated positively with peraluminosity (A/CNK), P2O5 content, and increasing temperature at temperatures above that of the glass transition. These structural relationships among phosphate complexes are coupled with decreasing polymerization of the aluminosilicate melts

Density of some titanium-bearing silicate liquids and the compositional dependence of the partial molar volume of TiO2

The densities of thirteen silicate liquids along the Na2SiO3-TiO2 and CaSiO3-TiO2 joins and six other titanium-bearing silicate liquids of the general formula TiSiO5 (where X = Li, Na, K, Rb, Cs, Ca, Sr, Ba) have been measured in equilibrium with air using the double Pt bob Archimedean method. The Na2SiO3-TiO2 join was investigated from 10–50 mole% TiO2 in the temperature range 1000–1150°C whereas the CaSiO3-TiO2 join was investigated from 10–80 mole% TiO2 in the temperature range of 1400–1625°C. Density increases with TiO2 content along both joins. Partial molar volumes of the binary endmembers, Na2SiO3 and CaSiO3, and of TiO2 have been computed. The partial molar volume of Na2SiO3 agrees well with that determined by Bockris et al. (1955). The partial molar volume of CaSiO3 is in disagreement with that of Tomlinson et al. (1958). The partial molar volume of TiO2 derived from a linear fit to the Na2SiO3-TiO2 join is 27.6(3) cm3/mole at 1150°C. The partial molar volume of TiO2 derived from linear extrapolation of the CaSiO3-TiO2 data to TiO2 at 1600°C is 24.3(4) cm3/mole. Comparison of the partial molar volume data from these binary joins with TiO2 liquid density data (Dingwell, 1991) requires the existence of a large positive excess volume in the Na2SiO3-TiO2 system at 1150°C

Polyhedral units and network connectivity in calcium aluminosilicate glasses from high-energy x-ray diffraction

Structure factors for Cax/2AlxSi1-xO2 glasses (x=0,0.25,0.5,0.67) extended to a wave vector of magnitude Q= 40 1/A have been obtained by high-energy x-ray diffraction. For the first time, it is possible to resolve the contributions of Si-O, Al-O and Ca-O coordination polyhedra to the experimental atomic pair distribution functions (PDF). It has been found that both Si and Al are four-fold coordinated and so participate in a continuous tetrahedral network at low values of x. The number of network breaking defects in the form of non-bridging oxygens (NBO's) increases slowly with x until x=0.5 (NBO's ~ 10% at x=0.5). By x=0.67 the network breaking defects become significant as evidenced by the significant drop in the average coordination number of Si. By contrast, Al-O tetrahedra remain free of NBO's and fully integrated in the Al/Si-O network for all values of x. Calcium maintains a rather uniform coordination sphere of approximately 5 oxygen atoms for all values of x. The results suggest that not only Si/Al-O tetrahedra but Ca-O polyhedra, too, play a role in determining the glassy structure