Helium in solubility equilibrium with quartz and porefluids in rocks - a new approach in hydrology

Quartz crystals in sandstones at depths of 1200 m–1400 m below the surface appear to reach a solubility equilibrium with the 4He-concentration in the surrounding pore- or groundwater after some time. A rather high 4Heconcentration of 4.5x10E-3 cc STP 4He/cm3 of water measured in a groundwater sample would for instance maintain a He pressure of 0.47 atm in a related volume. This value is equal within analytical error to the pressure deduced from the measured helium content of the quartz and its internal helium-accessible volume. To determine this volume, quartz crystals of 0.1 to 1 mm were separated from sandstones and exposed to a helium gas pressure of 32 atm at a temperature of 290°C for up to 2 months. By crushing, melting or isothermal heating the helium was then extracted from the helium saturated samples. Avolume on the order of 0.1% of the crystal volume is only accessible to helium atoms but not to argon atoms or water molecules. By monitoring the diffusive loss of He from the crystals at 350°C an effective diffusion constant on the order of 10E-9 cm2/s is estimated. Extrapolation to the temperature of 70°C in the sediments at a depth of 1400 m gives a typical time of about 100 000 years to reach equilibrium between helium in porewaters and the internal He-accessible volume of quartz crystals. In a geologic situation with stagnant pore- or groundwaters in sediments it therefore appears to be possible with this new method to deduce a 4He depth profile for porewaters in impermeable rocks based on their mineral record.

Equilibrium diagrams for minerals at low temperature and pressure.

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Interpretation of the temperature dependence of equilibrium and rate constants

The objective of this review is to draw attention to potential pitfalls in attempts to glean mechanistic information from the magnitudes of standard enthalpies and entropies derived from the temperature dependence of equilibrium and rate constants for protein interactions. Problems arise because the minimalist model that suffices to describe the energy differences between initial and final states usually comprises a set of linked equilibria, each of which is characterized by its own energetics. For example, because the overall standard enthalpy is a composite of those individual values, a positive magnitude for AHO can still arise despite all reactions within the subset being characterized by negative enthalpy changes: designation of the reaction as being entropy driven is thus equivocal. An experimenter must always bear in mind the fact that any mechanistic interpretation of the magnitudes of thermodynamic parameters refers to the reaction model rather than the experimental system For the same reason there is little point in subjecting the temperature dependence of rate constants for protein interactions to transition-state analysis. If comparisons with reported values of standard enthalpy and entropy of activation are needed, they are readily calculated from the empirical Arrhenius parameters. Copyright (c) 2006 John Wiley & Sons, Ltd.

Departure of high temperature iron lines from the equilibrium state in flaring solar plasmas

The aim of this study is to clarify if the assumption of ionization equilibrium and a Maxwellian electron energy distribution is valid in flaring solar plasmas. We analyze the 2014 December 20 X1.8 flare, in which the \ion{Fe}{xxi} 187~\AA, \ion{Fe}{xxii} 253~\AA, \ion{Fe}{xxiii} 263~\AA\ and \ion{Fe}{xxiv} 255~\AA\ emission lines were simultaneously observed by the EUV Imaging Spectrometer onboard the Hinode satellite. Intensity ratios among these high temperature Fe lines are compared and departures from isothermal conditions and ionization equilibrium examined. Temperatures derived from intensity ratios involving these four lines show significant discrepancies at the flare footpoints in the impulsive phase, and at the looptop in the gradual phase. Among these, the temperature derived from the \ion{Fe}{xxii}/\ion{Fe}{xxiv} intensity ratio is the lowest, which cannot be explained if we assume a Maxwellian electron distribution and ionization equilibrium, even in the case of a multi-thermal structure. This result suggests that the assumption of ionization equilibrium and/or a Maxwellian electron energy distribution can be violated in evaporating solar plasma around 10MK.

Temperature fields in a channel partially filled with a porous material under local thermal non-equilibrium condition-an exact solution

This work examines analytically the forced convection in a channel partially filled with a porous material and subjected to constant wall heat flux. The Darcy–Brinkman–Forchheimer model is used to represent the fluid transport through the porous material. The local thermal non-equilibrium, two-equation model is further employed as the solid and fluid heat transport equations. Two fundamental models (models A and B) represent the thermal boundary conditions at the interface between the porous medium and the clear region. The governing equations of the problem are manipulated, and for each interface model, exact solutions, for the solid and fluid temperature fields, are developed. These solutions incorporate the porous material thickness, Biot number, fluid to solid thermal conductivity ratio and Darcy number as parameters. The results can be readily used to validate numerical simulations. They are, further, applicable to the analysis of enhanced heat transfer, using porous materials, in heat exchangers.

Re-melting of Bi-2212/Ag laminated tapes by partial melting process

Bi-2212 tapes are prepared by a combination of dip-coating and partial melt processing. We investigate the effect of re-melting of those tapes by partial melting followed by slow cooling on the structure and superconducting properties. Microstructural studies of re-melted samples show that they have the same overall composition as partially melted tapes. However, the fractional volumes of the secondary phases differ and the amounts and distribution of the secondary phases have a significant effect on the critical current. Critical current of Bi-2212/Ag tapes strongly depends on the maximum processing temperature. Initial J(c)'s of the tapes, which are partially melted, then slowly solidified at optimum conditions and finally post-annealed in an inert atmosphere, are up to 10.4 x 10(3) A/cm(2). It is found that the maximum processing temperature at initial partial melting has an influence on the optimum re-heat treatment conditions for the tapes. Re-melted tapes processed at optimum conditions recover superconducting properties after post-annealing in an inert atmosphere: the J(c) values of the tapes are about 80-110% of initial J(c)'s of those tapes.

Si quantum dots embedded in an amorphous SiC matrix : nanophase control by non-equilibrium plasma hydrogenation

Nanophase nc-Si/a-SiC films that contain Si quantum dots (QDs) embedded in an amorphous SiC matrix were deposited on single-crystal silicon substrates using inductively coupled plasma-assisted chemical vapor deposition from the reactive silane and methane precursor gases diluted with hydrogen at a substrate temperature of 200 °C. The effect of the hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen-to-silane plus methane gases), ranging from 0 to 10.0, on the morphological, structural, and compositional properties of the deposited films, is extensively and systematically studied by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, Fourier-transform infrared absorption spectroscopy, and X-ray photoelectron spectroscopy. Effective nanophase segregation at a low hydrogen dilution ratio of 4.0 leads to the formation of highly uniform Si QDs embedded in the amorphous SiC matrix. It is also shown that with the increase of X, the crystallinity degree and the crystallite size increase while the carbon content and the growth rate decrease. The obtained experimental results are explained in terms of the effect of hydrogen dilution on the nucleation and growth processes of the Si QDs in the high-density plasmas. These results are highly relevant to the development of next-generation photovoltaic solar cells, light-emitting diodes, thin-film transistors, and other applications.

Extremely non-equilibrium synthesis of luminescent zinc oxide nanoparticles through energetic ion condensation in a dense plasma focus device

Luminescent ZnO nanoparticles have been synthesized on silicon and quartz substrates under extremely non-equilibrium conditions of energetic ion condensation during the post-focus phase in a dense plasma focus (DPF) device. Ar+, O+, Zn+ and ZnO+ ions are generated as a result of interaction of hot and dense argon plasma focus with the surfaces of ZnO pellets placed at the anode. It is found that the sizes, structural and photoluminescence (PL) properties of the ZnO nanoparticles appear to be quite different on Si(1 0 0) and quartz substrates. The results of x-ray diffractometry and atomic force microscopy show that the ZnO nanoparticles are crystalline and range in size from 5-7 nm on Si(1 0 0) substrates to 10-38 nm on quartz substrates. Room-temperature PL studies reveal strong peaks related to excitonic bands and defects for the ZnO nanoparticles deposited on Si (1 0 0), whereas the excitonic bands are not excited in the quartz substrate case. Raman studies indicate the presence of E2 (high) mode for ZnO nanoparticles deposited on Si(1 0 0).

Parameters and equilibrium profiles for large-area surface-wave sustained plasmas

The equilibrium profiles of the plasma parameters of large-area if discharges in a finite-length metal-shielded dielectric cylinder are computed using a two-dimensional fluid code. The rf power is coupled to the plasma through edge-localized surface waves traveling in the azimuthal direction along the plasma edge. It is shown that self-consistent accounting for axial plasma diffusion and radial nonuniformity of the electron temperature can explain the frequently reported deviations of experimentally measured radial density profiles from that of the conventional linear diffusion models. The simulation results are in a good agreement with existing experimental data obtained from surface-wave sustained large-diameter plasmas. © 2002 The American Physical Society.

The Cougar Point tuff: Implications for thermochemical zonation and longevity of high-temperature, large-volume silicic magmas of the Miocene Yellowstone hotspot

The 12.7-10.5 Ma Cougar Point Tuff in southern Idaho, USA, consists of 10 large-volume (>10²-10³ km³ each), high-temperature (800-1000 °C), rhyolitic ash-flow tuffs erupted from the Bruneau-Jarbidge volcanic center of the Yellowstone hotspot. These tuffs provide evidence for compositional and thermal zonation in pre-eruptive rhyolite magma, and suggest the presence of a long-lived reservoir that was tapped by numerous large explosive eruptions. Pyroxene compositions exhibit discrete compositional modes with respect to Fe and Mg that define a linear spectrum punctuated by conspicuous gaps. Airfall glass compositions also cluster into modes, and the presence of multiple modes indicates tapping of different magma volumes during early phases of eruption. Equilibrium assemblages of pigeonite and augite are used to reconstruct compositional and thermal gradients in the pre-eruptive reservoir. The recurrence of identical compositional modes and of mineral pairs equilibrated at high temperatures in successive eruptive units is consistent with the persistence of their respective liquids in the magma reservoir. Recurrence intervals of identical modes range from 0.3 to 0.9 Myr and suggest possible magma residence times of similar duration. Eruption ages, magma temperatures, Nd isotopes, and pyroxene and glass compositions are consistent with a long-lived, dynamically evolving magma reservoir that was chemically and thermally zoned and composed of multiple discrete magma volumes.

Finite Element Solution Of Surface-Tension Driven Flows In Laser Surface-Melting

Lasers are very efficient in heating localized regions and hence they find a wide application in surface treatment processes. The surface of a material can be selectively modified to give superior wear and corrosion resistance. In laser surface-melting and welding problems, the high temperature gradient prevailing in the free surface induces a surface-tension gradient which is the dominant driving force for convection (known as thermo-capillary or Marangoni convection). It has been reported that the surface-tension driven convection plays a dominant role in determining the melt pool shape. In most of the earlier works on laser-melting and related problems, the finite difference method (FDM) has been used to solve the Navier Stokes equations [1]. Since the Reynolds number is quite high in these cases, upwinding has been used. Though upwinding gives physically realistic solutions even on a coarse grid, the results are inaccurate. McLay and Carey have solved the thermo-capillary flow in welding problems by an implicit finite element method [2]. They used the conventional Galerkin finite element method (FEM) which requires that the pressure be interpolated by one order lower than velocity (mixed interpolation). This restricts the choice of elements to certain higher order elements which need numerical integration for evaluation of element matrices. The implicit algorithm yields a system of nonlinear, unsymmetric equations which are not positive definite. Computations would be possible only with large mainframe computers.Sluzalec [3] has modeled the pulsed laser-melting problem by an explicit method (FEM). He has used the six-node triangular element with mixed interpolation. Since he has considered the buoyancy induced flow only, the velocity values are small. In the present work, an equal order explicit FEM is used to compute the thermo-capillary flow in the laser surface-melting problem. As this method permits equal order interpolation, there is no restriction in the choice of elements. Even linear elements such as the three-node triangular elements can be used. As the governing equations are solved in a sequential manner, the computer memory requirement is less. The finite element formulation is discussed in this paper along with typical numerical results.

The effect of ball milling on the melting behavior of Sn-Cu-Ag eutectic alloy

Sn-Ag-Cu (SAC) solder alloys are the best Pb free alternative for electronic industry. Since their introduction, efforts are made to improve their efficacies by tuning the processing and composition to achieve lower melting point and better wettability. Nanostructured alloys with large boundary content are known to depress the melting points of metals and alloys. In this article we explore this possibility by processing prealloyed SAC alloys close to SAC305 composition (Sn-3wt%Ag-0.5wt%Cu) by mechanical milling which results in the formation of nanostructured alloys. Pulverisette ball mill (P7) and Vibratory ball mills are used to carry out the milling of the powders at room temperature and at lower temperatures (-104 A degrees C), respectively. We report a relatively smaller depression of melting point ranging up to 5 A degrees C with respect to original alloys. The minimum grain sizes achieved and the depression of melting point are similar for both room temperature and low-temperature processed samples. An attempt has been made to rationalize the observations in terms of the basic processes occurring during the milling.

Stability of pargasite during ultrahigh-temperature metamorphism:A consequence of titanium and REE partitioning

Orthopyroxene-clinopyroxene-plagioclase needles and symplectite along the cleavage planes and grain boundaries of fluorine-bearing titanian-ferroan pargasite from the Highland Complex, Sri Lanka, are interpreted as evidence for dehydration melting at ultrahigh-temperature conditions. High Ti (up to 0.4 pfu) and F (XF up to 0.56) content in pargasite extends its stability to higher temperatures, and the composition indicates the dehydration melting reaction may take place at ultrahigh-temperatures (~950 °C) at a pressure around 10 kbar, close to peak metamorphic conditions. The increase of Ti content close to the grain boundaries and cleavage planes in pargasite indicates titanium partitioning from the melt during dehydration melting enhanced the stability of the mineral toward ultrahigh-temperature conditions. The REE content in the pargasite shows a similar behavior to that of titanium. The cores with no breakdown assemblage consist of low and flat REE concentrations with respect to the high and Eu-depleted rim. Clinopyroxene in symplectite and needle-shaped lamellae within the pargasite porphyroblasts have similar REE patterns with slightly low-concentrations relative to that of pargasite. In the breakdown assemblage, LREEs are partitioned mainly into plagioclase while the HREEs are partitioned into orthopyroxene. The REE enrichment in the pargasite rims signals their relative partitioning between pargasite rims and melt. Modeling of the partitioning of Ti and REEs associated with pargasite breakdown demonstrates that its stability is greatly enhanced at UHT conditions. This investigation implies that the stability of hydrous minerals such as amphibole can be extended to UHT conditions, and expands our knowledge of metamorphism in the lower crust.

The nature of non-equilibrium solidification of undercooled Agsingle bondCu alloys in contact with primary copper dendrites

Liquids of silver-copper alloys with near eutectic compositions embedded in a copper matrix were undercooled. The structural and microstructural investigations of these alloys solidified from undercooled temperature indicated the absence of both the eutectic reaction and diffusionless transformation below the equal free energy curve (T0). Instead the liquid maintained local equilibrium with the copper dendrites continuously until it intersected the extended solidus of the silver rich solid solution.

Experimental Studies on Drop Formation at the Tip of Melting Rods

Drop formation at the conical tips of melting rods has been experimentally studied using the transparent wax-alcohol/acetonitrile system. The effects of cone angle, rod diameter, immersion depth, and bath temperature on the detached drop mass have been studied over a wide range, besides recording useful qualitative information based on visual observation. The experimental results suggest that the phenomenon of drop formation at the tip of melting rods has a close parallel with the drop formation at conical tips, at least on a qualitative basis. However, the results could not be quantified owing to difficulties in characterizing the physical properties of the system, despite efforts to minimize them.