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The abundance of coexisting structural units in K-, Na-, and Li-silicate melts and glasses from 25° to 1654°C has been determined with in-situ micro-Raman spectroscopy. From these data an equilibrium constant, Kx, for the disproportionation reaction among the structural units coexisting in the melts, Si2O5(2Q3)SiO3(Q2)+SiO2(Q4), was calculated (Kx is the equilibrium constant derived by using mol fractions rather than activities of the structural units). From ln Kx vs l/T relationships the enthalpy (Hx) for the disproportionation reaction is in the range of-30 to 30 kJ/mol with systematic compositional dependence. In the potassium and sodium systems, where the disproportionation reaction shifts to the right with increasing temperature, the Hx increases with silica content (M/Si decreases, M=Na, K). For melts and supercooled liquids of composition Li2O·2SiO2 (Li/Si=1), the Hx is indistinguishable from 0. By decreasing the Li/Si to 0.667 (composition LS3) and beyond (e.g., LS4), the disproportionation reaction shifts to the left as the temperature is increased. For a given ratio of M/Si (M=K, Na, Li), there is a positive, near linear correlation between the Hx and the Z/r2 of the metal cation. The slope of the Hx vs Z/r2 regression lines increases as the system becomes more silica rich (i.e., M/Si is decreased). Activity coefficients for the individual structural units, i, were calculated from the structural data combined with liquidus phase relations. These coefficients are linear functions of their mol fraction of the form i=a lnX i+b, where a is between 0.6 and 0.87, and X i is the mol fraction of the unit. The value of the intercept, b, is near 0. The relationship between activity coefficients and abundance of individual structural units is not affected by temperature or the electronic properties of the alkali metal. The activity of the structural units, however, depend on their concentration, type of metal cation, and on temperature.  相似文献   
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 Premelting effects in gehlenite (Ca2Al2SiO7) have been studied by Raman spectroscopy and calorimetry, and in gehlenite and pseudowollastonite (CaSiO3) by electrical conductivity. The enthalpy of premelting of gehlenite is 17.3 kJ mol−1 and represents 9% of the reported enthalpy of fusion, which is in the range of the reported fraction of other minerals. The Raman and electrical conductivity experiments at high temperatures, for gehlenite and pseudowollastonite, show that the premelting effects of both compositions are associated with enhanced dynamics of calcium atoms near the melting point. This conclusion agrees with the results obtained for other minerals like diopside, but contrasts with those found for sodium metasilicate in which the weaker bonding of sodium allows the silicate framework to distort near the melting temperature and deform in such a way to prefigure the silicate entities present in the melt. Received: 30 April 2002 / Accepted: 7 August 2002 Acknowledgements We thank Y. Linard for help with DSC measurements and two anonymous reviewers for their constructive comments. This work has been partly supported by the EU Marie-Curie fellowship contract no. HPMF-CT-1999-00329, the CNRS-Carnegie Institution of Washington program PICS no.192, and the NSF grants EAR-9614432 and EAR-9901886 to B.O.M.  相似文献   
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Large-eddy simulations of a clear convective boundary layer (CBL)and a stratocumulus-topped boundary layer are studied. Bottom-upand a top-down scalars were included in the simulations, and theprinciple of linear superposition of variables was applied toreconstruct the fields of any arbitrary conserved variable.This approach allows a systematic analysis of countergradient fluxesas a function of the flux ratio, which is defined as the ratio betweenthe entrainment flux and the surface flux of the conserved quantity.In general, the turbulent flux of an arbitrary conserved quantityis counter to the mean vertical gradient if the heights where thevertical flux and the mean vertical gradient change sign do notcoincide. The regime where the flux is countergradient is thereforebounded by the so-called zero-flux and zero-gradient heights. Becausethe vertical flux changes sign only if the entrainment flux has anopposite sign to the surface flux, countergradient fluxes arepredominantly found for negative flux ratios. In the CBL the fluxratio for the virtual potential temperature is, to a good approximation,constant, and equal to -0.2. Only if the moisture contribution to thevirtual potential temperature is negligibly small will the flux ratio forthe potential temperature be equal to this value. Otherwise, theflux ratio for the potential temperature can have any arbitrary(negative) value, and, as a consequence, the fluxes for thepotential temperature and the virtual potential temperature willbe countergradient at different heights. As a practical application ofthe results, vertical profiles of the countergradient correction termfor different entrainment-to-surface-flux ratios are discussed.  相似文献   
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The structures of sodium silicate and aluminosilicate glasses quenched from melts at high pressure (6-10 GPa) with varying degrees of polymerization (fractions of nonbridging oxygen) were explored using solid-state NMR [17O and 27Al triple-quantum magic-angle spinning (3QMAS) NMR]. The bond connectivity in melts among four and highly coordinated network polyhedra, such as [4]Al, [5,6]Al, [4]Si, and [5,6]Si, at high pressure is shown to be significantly different from that at ambient pressure. In particular, in the silicate and aluminosilicate melts, the proportion of nonbridging oxygen (NBO) generally decreases with increasing pressure, leading to the formation of new oxygen clusters that include 5- and 6-coordinated Si and Al in addition to 4-coordinated Al and Si, such as [4]Si-O-[5,6]Si, [4]Si-O-[5,6]Al and Na-O-[5,6]Si. While the fractions of [5,6]Al increase with pressure, the magnitude of this increase diminishes with increasing degrees of ambient-pressure polymerization under isobaric conditions. Incorporating the above structural information into models of melt properties reproduces the anomalous pressure-dependence of O2− diffusivity and viscosity often observed in silicate melts.  相似文献   
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Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na2O-SiO2-H2O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂XH2O, decreases with increasing total water content. At low water contents, the influence of H2O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q4-species to form Q3 and Q2 species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q3-species react with water to form Q2-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published 1H and 29Si MAS NMR and 1H-29Si cross polarization NMR data.  相似文献   
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