Crystal chemistry of a new solid solution in the BaO-Bi2O3-Nb2O5 system: Ba-5x/2-Bi(1-x)5/3Nb5O15

A solid solution of the type Ba5x/2Bi(1-x)5/3Nb5O15 has been identified in the BaO-Bi2O3-Nb2O5 system for the first time. The limits of the solid solution are within the range 0.52 <= x <= 0.80. The compositions x = 0.52, 0.60, 0.72, 0.77, 0.78, and 0.80 were synthesized by the solid-state technique from the starting materials in stoichiometric quantities. The powder X-ray patterns of all the phases in the domain indicate a structural similarity to tetragonal tungsten bronzes (TTBs). The compositions below x = 0.52 and those above x = 0.80 exhibit barium niobate and bismuth niobate impurities, respectively. Single crystals of the composition x = 0.77 were obtained by the melt cooling technique. The crystal structure of Ba3.85/2Bi1.15/3Nb5O15 (x = 0.77) was solved in the tetragonal space group P4bm (No. 100) with a = 12.4938 (14) angstrom, c = 3.9519 (2) A, V = 616.87 (10) angstrom(3), and Z = 2 and was refined to an R index of 0.034. Dielectric measurements on all the phases indicate a typical relaxor behavior with a broad phase transition at T-m approximate to 300 K.

Crystal structure and ionic conductivity of a new bismuth tungstate,Bi3W2O10.5

The compound Bi3W2O10.5 was synthesized by the solid-state technique from Bi2O3 and WO3 in stoichiometric quantities. Single crystals were grown by the melt-cooling technique and the crystal structure was solved in the tetragonal 141in space group with a = 3.839 (1) A, c = 16-3S2 (5) A, V = 241.4 (1) angstrom(3), Z = 4 and was refined to an R index of 0.0672. The structure represents a modification of the Aurivillius phase and consists of [Bi2O2](2+) units separated by WO8 polyhedra. a.c. impedance studies indicate oxide ion conductivity of 2.91 10(-5) cm(-1) at 600 degrees C.

Geochemistry and petrology of the ferropicrite dikes and associated rocks of Vestfjella, western Dronning Maud Land, Antarctica

This study provides insights into the composition and origin of ferropicrite dikes (FeOtot = 13 17 wt. %; MgO = 13 19 wt. %) and associated meimechite, picrite, picrobasalt, and basalt dikes found at Vestfjella, western Dronning Maud Land, Antarctica. The dikes crosscut Jurassic Karoo continental flood basalts (CFB) that were emplaced during the early stages of the breakup of the Gondwana supercontinent ~180 Ma ago. Selected samples (31 overall from at least eleven dikes) were analyzed for their mineral chemical, major element, trace element, and Sr, Nd, Pb, and Os isotopic compositions. The studied samples can be divided into two geochemically distinct types: (1) The depleted type (24 samples from at least nine dikes) is relatively depleted in the most incompatible elements and exhibits isotopic characteristics (e.g., initial εNd of +4.8 to +8.3 and initial 187Os/188Os of 0.1256 0.1277 at 180 Ma) similar to those of mid-ocean ridge basalts (MORB); (2) The enriched type (7 samples from at least two dikes) exhibits relatively enriched incompatible element and isotopic characteristics (e.g., initial εNd of +1.8 to +3.6 and initial 187Os/188Os of 0.1401 0.1425 at 180 Ma) similar to those of oceanic island basalts. Both magma types have escaped significant contamination by the continental crust. The depleted type is related to the main phase of Karoo magmatism and originated as highly magnesian (MgO up to 25 wt. %) partial melts at high temperatures (mantle potential temperature >1600 °C) and pressures (~5 6 GPa) from a sublithospheric, water-bearing, depleted peridotite mantle source. The enriched type sampled pyroxene-bearing heterogeneities that can be traced down to either recycled oceanic crust or melt-metasomatized portions of the sublithospheric or lithospheric mantle. The source of the depleted type represents a sublithospheric end-member source for many Karoo lavas and has subsequently been sampled by the MORBs of the Indian Ocean. These observations, together with the purported high temperatures, indicate that the Karoo CFBs were formed in an extensive melting episode caused mainly by internal heating of the upper mantle beneath the Gondwana supercontinent. My research supports the view that ferropicritic melts can be generated in several ways: the relative Fe-enrichment of mantle partial melts is most readily achieved by (1) relatively low degree of partial melting, (2) high pressure of partial melting, and (3) melting of enriched source components (e.g., pyroxenite and metasomatized peridotite). Ferropicritic whole-rock compositions could also result from accumulation, secondary alteration, and fractional crystallization, however, and caution is required when addressing the parental magma composition.

Carbon dioxide and methane exchange between a boreal pristine lake and the atmosphere

Lakes serve as sites for terrestrially fixed carbon to be remineralized and transferred back to the atmosphere. Their role in regional carbon cycling is especially important in the Boreal Zone, where lakes can cover up to 20% of the land area. Boreal lakes are often characterized by the presence of a brown water colour, which implies high levels of dissolved organic carbon from the surrounding terrestrial ecosystem, but the load of inorganic carbon from the catchment is largely unknown. Organic carbon is transformed to methane (CH4) and carbon dioxide (CO2) in biological processes that result in lake water gas concentrations that increase above atmospheric equilibrium, thus making boreal lakes as sources of these important greenhouse gases. However, flux estimates are often based on sporadic sampling and modelling and actual flux measurements are scarce. Thus, the detailed temporal flux dynamics of greenhouse gases are still largely unknown. ----- One aim here was to reveal the natural dynamics of CH4 and CO2 concentrations and fluxes in a small boreal lake. The other aim was to test the applicability of a measuring technique for CO2 flux, i.e. the eddy covariance (EC) technique, and a computational method for estimation of primary production and community respiration, both commonly used in terrestrial research, in this lake. Continuous surface water CO2 concentration measurements, also needed in free-water applications to estimate primary production and community respiration, were used over two open water periods in a study of CO2 concentration dynamics. Traditional methods were also used to measure gas concentration and fluxes. The study lake, Valkea-Kotinen, is a small, humic, headwater lake within an old-growth forest catchment with no local anthropogenic disturbance and thus possible changes in gas dynamics reflect the natural variability in lake ecosystems. CH4 accumulated under the ice and in the hypolimnion during summer stratification. The surface water CH4 concentration was always above atmospheric equilibrium and thus the lake was a continuous source of CH4 to the atmosphere. However, the annual CH4 fluxes were small, i.e. 0.11 mol m-2 yr-1, and the timing of fluxes differed from that of other published estimates. The highest fluxes are usually measured in spring after ice melt but in Lake Valkea-Kotinen CH4 was effectively oxidised in spring and highest effluxes occurred in autumn after summer stratification period. CO2 also accumulated under the ice and the hypolimnetic CO2 concentration increased steadily during stratification period. The surface water CO2 concentration was highest in spring and in autumn, whereas during the stable stratification it was sometimes under atmospheric equilibrium. It showed diel, daily and seasonal variation; the diel cycle was clearly driven by light and thus reflected the metabolism of the lacustrine ecosystem. However, the diel cycle was sometimes blurred by injection of hypolimnetic water rich in CO2 and the surface water CO2 concentration was thus controlled by stratification dynamics. The highest CO2 fluxes were measured in spring, autumn and during those hypolimnetic injections causing bursts of CO2 comparable with the spring and autumn fluxes. The annual fluxes averaged 77 (±11 SD) g C m-2 yr-1. In estimating the importance of the lake in recycling terrestrial carbon, the flux was normalized to the catchment area and this normalized flux was compared with net ecosystem production estimates of -50 to 200 g C m-2 yr-1 from unmanaged forests in corresponding temperature and precipitation regimes in the literature. Within this range the flux of Lake Valkea-Kotinen yielded from the increase in source of the surrounding forest by 20% to decrease in sink by 5%. The free water approach gave primary production and community respiration estimates of 5- and 16-fold, respectively, compared with traditional bottle incubations during a 5-day testing period in autumn. The results are in parallel with findings in the literature. Both methods adopted from the terrestrial community also proved useful in lake studies. A large percentage of the EC data was rejected, due to the unfulfilled prerequisites of the method. However, the amount of data accepted remained large compared with what would be feasible with traditional methods. Use of the EC method revealed underestimation of the widely used gas exchange model and suggests simultaneous measurements of actual turbulence at the water surface with comparison of the different gas flux methods to revise the parameterization of the gas transfer velocity used in the models.

Svekofennialaisen orogenian ylityönnön terminen mallinnus Itä-Suomen arkeeisella kratonilla

This study reviews the thermophysical properties of rocks and the lithosphere and describes a one dimensional thermal numeric model of hypothetical 20 km thick overthrust plate obtruded on to the Archeaen craton in the Svecofennian orogeny (1.92-1.77 Ga). The objective is to find out if the overthrust plate and its radiogenic heat sources were able to produce the thermal effects observed on the current erosion level of the Archaean craton. Heat transfer in lithosphere is assumed conductive, and advective heat transfer due to melting and melt transfer is supposed negligible. The study area is located in the Eastern Finland, approximately current Kainuu and Northern Karelia regions, east from the most active orogenic belt (Raahe-Ladoga zone), so that orogenic magmatism can be neglected. Physical parameters and boundary conditions for the model are from different earlier published sources: deep seismic profiles (rock variation in depth), laboratory measurements (heat production and conductivity of rocks), field measurements (heat flow densities), and pT(t) estimations from the Finnish precambrian to estimate the size and thickness of the sheet. Comparison of the modelling results to previous K-Ar datings and other pTt estimations show, that the effect of the overthrust sheet has been adequate (max. T 450°C at 4 kbar) to produce the K-Ar resetting ages measured from the Archaean bedrock at current erosion level. No other kind of thermal activation in lithosphere is required. Results show possibly very minor partial melting in upper middle crust underneath the overthrust sheet.

Numerical simulation of solidification of liquid aluminum alloy flowing on cooling slope

Preparation of semisolid slurry using a cooling slope is increasingly becoming popular, primarily because of the simplicity in design and ease control of the process. In this process, liquid alloy is poured down an inclined surface which is cooled from underneath. The cooling enables partial solidification and the incline provides the necessary shear for producing semisolid slurry. However, the final microstructure of the ingot depends on several process parameters such as cooling rate, incline angle of the cooling slope, length of the slope and initial melt superheat. In this work, a CFD model using volume of fluid (VOF) method for simulating flow along the cooling slope was presented. Equations for conservation of mass, momentum, energy and species were solved to predict hydrodynamic and thermal behavior, in addition to predicting solid fraction distribution and macrosegregation. Solidification was modeled using an enthalpy approach and a volume averaged technique for the different phases. The mushy region was modeled as a multi-layered porous medium consisting of fixed columnar dendrites and mobile equiaxed/fragmented grains. The alloy chosen for the study was aluminum alloy A356, for which adequate experimental data were available in the literature. The effects of two key process parameters, namely the slope angle and the pouring temperature, on temperature distribution, velocity distribution and macrosegregation were also studied.

Induction reheating of A356.2 aluminum alloy and thixocasting as automobile component

The development work for producing an automobile component by thixocasting using A356.2 alloy was introduced. As the first step, the alloy was electromagnetically stirred and solidified to produce a billet with non-dendritic microstructure. The microstructure depended on several process parameters such as stirring intensity, stirring frequency, cooling rate, and melt initial superheat. Through a series of computational studies and controlled experiments, a set of process parameters were identified to produce the best microstructures. Reheating of a billet with non-dendritic microstructure to a semisolid temperature was the next step for thixo-casting of the components. The reheating process was characterized for various reheating cycles using a vertical-type reheating machine. The induction heating cycle was optimized to obtain a near-uniform temperature distribution in radial as well as axial direction of the billet, and the heating was continued until the liquid fraction reached about 50%. These parameters were determined with the help of a computational fluid dynamics (CFD) model of die filling and solidification of the semisolid alloy. The heated billets were subsequently thixo-cast into automobile components using a real-time controlled die casting machine. The results show that the castings are near net shape, free from porosity, good surface finish and have superior mechanical properties compared to those produced by conventional die casting processes using the same alloy.

Heat transfer correlations for PCM-based heat sinks with plate fins

Characterization of melting process in a Phase Change Material (PCM)-based heat sink with plate fin type thermal conductivity enhancers (TCEs) is numerically studied in this paper. Detailed parametric investigations are performed to find the effect of aspect ratio of enclosure and the applied heat flux on the thermal performance of the heat sinks. Various non-dimensional numbers, such as Nusselt number (Nu), Rayleigh number (Ra), Stefan number (Ste) and Fourier number (Fo) based on a characteristic length scale, are identified as important parameters. The half fin thickness and the fin height are varied to obtain a wide range of aspect ratios of an enclosure. It is found that a single correlation of Nu with Ra is not applicable for all aspect ratios of enclosure with melt convection taken into account. To find appropriate length scales, enclosures with different aspect ratios are divided into three categories, viz. (a) shallow enclosure, (b) rectangular enclosure and (c) tall enclosure. Accordingly, an appropriate characteristic length scale is identified for each type of enclosure and correlation of Nu with Ra based on that characteristic length scale is developed. (C) 2010 Elsevier Ltd. All rights reserved.

Formation of lead pyrophosphate glass and the role of anion disproportionation

Thermal, spectroscopic and electrical properties of lead pyrophosphate glass prepared by melt quenching have been examined. A model based on the structural disproportionation of the P2O 7 4− ions has been proposed and is shown to consistently explain all the observations. The equilibrium of various anionic species has been discussed on the basis of their electronegativities which are in turn related to their basicities.

Crystal Chemistry of the Noncentrosymmetric Eulytites: A(3)Bi(XO4)(3) (X = V, A = Pb; X = P, A = Ca, Cd, Sr, Pb)

Eulytite compounds, A(3)Bi(XO4)(3) (X = P, A = Ca, Cd, Sr, Pb), belong to the noncentrosymmetric space group l (4) over bar 3d (No. 220) as determined by single-crystal X-ray diffraction studies. The crystals were grown from the melt-cool technique with considerable difficulty as the compounds melt incongruently at their melting temperature, except for the compound Pb3Bi(PO4)(3). The unit cell parameter a is 9.984(5), 9.8611(3), 10.2035(3), and 10.3722(2) angstrom for Ca3Bi(PO4)(3), Cd3Bi(PO4)(3), Sr3Bi(PO4)(3), and Pb3Bi(PO4)(3) respectively, and there are four formula units in the unit cell. The structure of Pb3Bi(VO4)(3), a unique eulytite with vanadium substitution, is compared with all these phosphorus substituted eulytites. The A(2+) and Bi3+ cations occupy the special position (16c) while the O anions occupy the general Wyckoff position (48e) in the crystal structure. Only one O position has been identified for Pb3Bi(PO4)(3) and Pb3Bi(VO4)(3), whereas two O atom sites were identified for Ca3Bi(PO4)(3), Cd3Bi(PO4)(3), and Sr3Bi(PO4)(3). The UV-vis diffuse reflectance spectra indicate large band gaps for all the phosphate eulytites while a lower band gap is observed for the vanadate eulytite. The feasibility of the use of these compounds in optoelectronic devices has been tested by measuring the second-harmonic generation (SHG) values which have been found to be of a magnitude equivalent to the commercially used KDP (KH2PO4).

Heterogeneous nucleation of solidification of cadmium particles embedded in an aluminium matrix

A hypomonotectic alloy of Al-4.5wt%Cd has been manufactured by melt spinning and the resulting microstructure examined by transmission electron microscopy. As-melt spun hypomonotectic Al-4.5wt%Cd consists of a homogeneous distribution of faceted 5 to 120 nm diameter cadmium particles embedded in a matrix of aluminium, formed during the monotectic solidification reaction. The cadmium particles exhibit an orientation relationship with the aluminium matrix of {111}Al//{0001}Cd and lang110rangAlAl//lang11¯20> Cd, with four cadmium particle variants depending upon which of the four {111}Al planes is parallel to {0001}Cd. The cadmium particles exibit a distorted cuboctahedral shape, bounded by six curved {100}Al//{20¯23}Cd facets, six curved {111}Al/{40¯43}Cd facets and two flat {111}Al//{0001}Cd facets. The as-melt spun cadmium particle shape is metastable and the cadmium particles equilibrate during heat treatment below the cadmium melting point, becoming elongated to increase the surface area and decrease the separation of the {111}Al//{0001}Cd facets. The equilibrium cadmium particle shape and, therefore, the anisotropy of solid aluminium-solid cadmium and solid aluminium -liquid cadmium surface energies have been monitored by in situ heating in the transmission electron microscope over the temperature range between room temperature and 420 °C. The anisotropy of solid aluminium-solid cadmium surface energy is constant between room temperature and the cadmium melting point, with the {100}Al//{20¯23}Cd surface energy on average 40% greater than the {111}Al//{0001}Cd surface energy, and 10% greater than the {111}Al//{40¯43Cd surface energy. When the cadmium particles melt at temperatures above 321 °C, the {100}Al//{20¯23}Cd facets disappear and the {111}Al//{40¯43}Cd and {111}A1//{0001}Cd surface energies become equal. The {111}Al facets do not disappear when the cadmium particles melt, and the anisotropy of solid aluminium-liquid cadmium surface energy decreases gradually with increasing temperature above the cadmium melting point. The kinetics of cadmium solidification have been examined by heating and cooling experiments in a differential scanning calorimeter over a range of heating and cooling rates. Cadmium particle solidification is nucleated catalytically by the surrounding aluminium matrix on the {111}Al faceted surfaces, with an undercooling of 56 K and a contact angle of 42 °. The nucleation kinetics of cadmium particle solidification are in good agreement with the hemispherical cap model of heterogeneous nucleation.

Unfolding of Plasmodium falciparum triosephosphate isomerase in urea and guanidinium chloride solutions. Evidence for a novel disulfide exchange reaction in a covalently crosslinked mutant

The conformational stability of Plasmodium falciparum triosephosphate isomerase (TIMWT) enzyme has been investigated in urea and guanidinium chloride (GdmCl) solutions using circular dichroism, fluorescence, and size-exclusion chromatography. The dimeric enzyme is remarkably stable in urea solutions. It retains considerable secondary, tertiary, and quaternary structure even in 8 M urea. In contrast, the unfolding transition is complete by 2.4 M GdmCl. Although the secondary as well as the tertiary interactions melt before the perturbation of the quaternary structure, these studies imply that the dissociation of the dimer into monomers ultimately leads to the collapse of the structure, suggesting that the interfacial interactions play a major role in determining multimeric protein stability. The Cm(urea)/Cm(GdmCl) ratio (where Cm is the concentration of the denaturant required at the transition midpoint) is unusually high for triosephosphate isomerase as compared to other monomeric and dimeric proteins. A disulfide cross-linked mutant protein (Y74C) engineered to form two disulfide cross-links across the interface (13-74‘) and (13‘-74) is dramatically destablized in urea. The unfolding transition is complete by 6 M urea and involves a novel mechanism of dimer dissociation through intramolecular thiol−disulfide exchange.

Quasicrystalline and related crystalline phases in a rapidly solidified 2024-2Li aluminium alloy

The formation and decomposition of quasicrystalline and crystalline phases in as-rapidly solidified and annealed commercial AISI 2024 aluminum alloy containing 2 wt% Li have been investigated by detailed transmission electron microscopy, including a combination of bright field and dark field imaging, selected area diffraction pattern analysis and energy dispersive X-ray microanalysis. The microstructure of as-melt spun 2024-2Li consists of alpha-Al cells, containing small coherent delta' precipitates, and particles or a continuous network of the icosahedral phase at the cell boundaries. After annealing at 300-degrees-C, the intercellular particles of the icosahedral phase coarsen progressively and assume a more faceted shape; after annealing at 400-degrees-C, particles of the decagonal and crystalline O phases precipitate heterogeneously on preexisting particles of the icosahedral phase; and after annealling at 500-degrees-C, the icosahedral and decagonal phases dissolve completely, and small particles of the crystalline O phase remain together with newly precipitated plates of the T1 phase. The icosahedral phase in melt spun and melt spun/annealed 2024-2Li belongs to the Al6CuLi3 class of icosahedral phases, with a quasilattice constant of 0.51 nm, a stoichiometry of (Al, Si)6(Cu, Mn, Fe) (Li, Mg)3 and an average composition of Al-24.1 at.% Cu-6.4 at.% Mg-1.7 at.% Si-0.3 at.% Mn-0.5 at.% Fe as-melt spun and Al-21.9 at.% Cu-6.3 at.% Mg-1.0 at.% Si-0.5 at.% Fe as-heat-treated. The decagonal phase in melt spun/annealed 2024-2Li belongs to the Al4Mn class of decagonal phases, with a periodicity of 1.23 nm along the 10-fold symmetry axis, a stoichiometry of Al3(Cu, Mn, Fe) and an average composition of Al-10.3 at.% Cu-13.8 at.% Mn-2.3 at.% Fe. The crystalline O phase in melt spun/annealed 2024-2Li has an orthorhombic structure with lattice parameters of a = 2.24 nm, b = 2.35 nm and c = 1.23 nm, a stoichiometry of Al3(Cu, Mn, Fe) and an average composition of Al-11.0 at.% Cu-14.8 at.% Mn-3.9 at.% Fe. Detailed analysis of selected area diffraction patterns shows a close similarity between the icosahedral, decagonal and crystalline O phases in melt spun and melt spun/annealed 2024-2Li. In particular, the decagonal phase and crystalline O phases have a similar composition, and exhibit an orientation relationship which can be expressed as: [GRAPHICS] suggesting that the orthorhombic O phase is an approximant structure for the decagonal phase.

Dielectric and Impedance Studies on 0.5Li(2)O-0.5K(2)O-2B(2)O(3) Glasses

Transparent glasses in the system 0.5Li(2)O-0.5K(2)O-2B(2)O(3) (LKBO) were fabricated via the conventional melt quenching technique. Amorphous and glassy nature of the samples was confirmed by X-ray diffraction and differential scanning calorimetry (DSC) respectively. Complex dielectric and impedance studies were conducted on the samples at different temperatures in the 100 Hz-10 MHz frequency range. ac conductivity was calculated from the dielectric data and the conductivity relaxation was found to obey the Jonscher's law. The Nyquist's plots (Z `'(omega) vs. Z'(omega)) showed single suppressed semicircles at all the temperatures under study indicating the non ideal Debye type relaxation process to be active. Activation energies for conduction and relaxation process were calculated using the Arrhenius relation. The UV-visible optical transmission spectra was shown a wide transmission window and calculated optical band gap was found to be 5.67 eV.

An Investigation Of Alkali Aluminosilicate Glasses By Si-29 And Al-27 Magic-Angle-Spinning Nmr-Spectroscopy

Alkali aluminosilicate glasses prepared by the gel and the melt routes have been investigated by Si-29 and Al-27 MAS NMR spectroscopy. It is found that Al has a tetrahedral coordination in the gel glasses modified with equivalent proportions of alkalis unlike in a pure aluminosilicate glass where Al has both four and six coordinations. Silicon is present as Q4 units in all the 5M2O 5Al2O3 9OSiO2 ( M = Li, Na and K) gel glasses studied whereas it is present in Q2 or Q3 species in the lithium aluminosilicate glasses of compositions 40Li2O x Al2O3 (1-x)SiO2 (1 less-than-or-equal-to x less-than-or-equal-to 15) and xLi2O 10Al2O3 (1-x)SiO2 (20 less-than-or-equal-to x less-than-or-equal-to 40). The combination of Q2 and Q3 is also found in certain sodium aluminosilicate glasses, but they change to Q2 and Q1 as the concentration of SiO2 decreases.