A thermodynamic study of liquid Cu-Cr alloys and metastable liquid immiscibility

he thermodynamic acitivity of chromium in liquid Cu-Cr alloys is measured in the temperature range from 1473 to 1873 K using the solid state cell: Pt, W, Cr + Cr2O3 |(Y2O3) ThO2|Cu - Cr + Cr2O3, Pt The activity of copper and the Gibbs energy of mixing of the liquid alloy are derived. Activities exhibit large positive deviations from Raoult's law. The mixing properties can be represented by a pseudo-subregular solution model in which the excess entropy has the same type of functional dependence on composition as the enthalpy of mixing: ΔGE = XCr(1 - XCr)[60880 - 18750 XCr)-- T(16.25 - 7.55 XCr)]J mol-1 Pure liquid Cu and Cr are taken as the reference states. The results predict a liquid-liquid metastable miscibility gap, with TC = 1787 (±3) K and XCr = 0.436 (±0.02), lying below the liquidus. The results obtained in this study are in general agreement with experimental information reported in the literature, but provide further refinement of the thermodynamic parameters.

花岗岩-LiF-NaF-H_2O体系液相不混溶的实验研究

Liquid segregation phenomena have been found and explained in the F(Li)-rich granites in south China by Wang Linakui et al. (1979; 1983). A number of experimental investigations into the liquid immiscibilities in the granites systems have been carried out (Anfilogov et al., 1983; Glyuk et al., 1971; Glyuk et al., 1973a; 1973b; kovalenko, 1978; Wang Liangkui et al., 1987). Nevertheless, the detailed scenarios of the liquid immiscibilities in the granitic magmas are much less understood. This experimental study is amide to get access to this problem. Starting materials are biotite granite +LiF(3-10%)+NaF(3-10%)+H_2O(30%). The experimental results have shown that the liquid immiscibilities of melts of different compositions occur at 1 kbar and 840 ℃ when 5wt% (LiF + NaF) are added to the granite samples. three kinds of glasses indicating of three types of coexisting immiscible melts have been observed: light blue matrix glass, melanocratic glass balls and leucocratic glass balls. It is interesting that we have observed various kinds of textures as follows: spherulitic texture, droplets, flow bands, swirls. All these textures can be comparable to those in the natural granitic bodies. Electron microprobe data suggest that these different kinds of glasses are of different chemical compositions respectively; matrix glasses are F-poor silicate melts; melanocratic balls correspond to F-rich silicate melts; and leucocratic balls are the melts consisting mainly of fluorides. Raman spectrometric data have indicated that different glasses have different melt structures. TFM Diagrams at 1000 * 10~5 Pa have been plotted, in which two miscible gaps are found. One of the two gaps corresponds to the immiscibility between F - poor silicate melt and F-rich silicate melt, another to that between the silicate melt and fluoride melt. The experiments at different pressures have suggested that the decreases in pressures are favorable to the liquid immiscibility. Several reversal experiments have indicated that the equilibria in different runs have been achieved. We have applied the experimental results to explain the field evidence of immiscibilities in some of granites associated with W-Sn-Nb-Ta mineralization. These field phenomena include flow structure, globular structures,mineralized globular patche and glass inclusions in topaz. We believe that the liquid immiscibility (liquid segregation) is a possible way of generation of F(Li)-rich granites. During the evolution of the granitic magmas, the contents of Li, F, H_2O and ore-forming elements in the magmas become higher and higher. The granites formed in the extensional tectonic settings commonly bear higher abundences of the above-mentioned elements. the pressures of the granitic magmas are relatively lower during the processes of their emplacements and cooling. The late-staged magmas will produce liquid immiscibilities, leading to the production of several coexisting immiscible melts with different chemical compositions. The flow of immiscible consisting magmas will produce F(Li)-rich granites. It is also considered that liquid immiscibilities are of great significance in the production of rare metal granites. The ore-forming processes and magmatic crystallization and metasomatic processes can be occur at the same time. The mineralisations of rare metals are related to both magmatic and hydrothermal processes.

Alkaline magmatism in the Amambay area, NE Paraguay: The Cerro Sarambi complex

The Early Cretaceous alkaline magmatism in the northeastern region of Paraguay (Amambay Province) is represented by stocks, plugs, dikes, and dike swarms emplaced into Carboniferous to Triassic-Jurassic sediments and Precambrian rocks. This magmatism is tectonically related to the Ponta Pora Arch, a NE-trending structural feature, and has the Cerro Sarambi and Cerro Chiriguelo carbonatite complexes as its most significant expressions. Other alkaline occurrences found in the area are the Cerro Guazu and the small bodies of Cerro Apua, Arroyo Gasory, Cerro Jhu, Cerro Tayay, and Cerro Teyu. The alkaline rocks comprise ultramafic-mafic, syenitic, and carbonatitic petrographic associations in addition to lithologies of variable composition and texture occurring as dikes; fenites are described in both carbonatite complexes. Alkali feldspar and clinopyroxene, ranging from diopside to aegirine, are the most abundant minerals, with feldspathoids (nepheline, analcime), biotite, and subordinate Ti-rich garnet; minor constituents are Fe-Ti oxides and cancrinite as the main alteration product from nepheline. Chemically, the Amambay silicate rocks are potassic to highly potassic and have miaskitic affinity, with the non-cumulate intrusive types concentrated mainly in the saturated to undersaturated areas in silica syenitic fields. Fine-grained rocks are also of syenitic affiliation or represent more mafic varieties. The carbonatitic rocks consist dominantly of calciocarbonatites. Variation diagrams plotting major and trace elements vs. SiO(2) concentration for the Cerro Sarambi rocks show positive correlations for Al(2)O(3), K(2)O, and Rb, and negative ones for TiO(2), MgO, Fe(2)O(3), CaO, P(2)O(5), and Sr, indicating that fractional crystallization played an important role in the formation of the complex. Incompatible elements normalized to primitive mantle display positive spikes for Rb, La, Pb, Sr, and Sm, and negative for Nb-Ta, P, and Ti, as these negative anomalies are considerably more pronounced in the carbonatites. Chondrite-normalized REE patterns point to the high concentration of these elements and to the strong LRE/HRE fractionation. The Amambay rocks are highly enriched in radiogenic Sr and have T(DM) model ages that vary from 1.6 to 1.1 Ga. suggesting a mantle source enriched in incompatible elements by metasomatic events in Paleo-Mesoproterozoic times. Data are consistent with the derivation of the Cerro Sarambi rocks from a parental magma of lamprophyric (minette) composition and suggest an origin by liquid immiscibility processes for the carbonatites. (C) 2011 Elsevier Ltd. All rights reserved.

Petrografia, geocronologia e significado tectônico do Nefelina Sienito Brejinho: extremo noroeste da Província Borborema

No extremo noroeste da Província Borborema foi identificado um maciço alcalino subsaturado, o Nefelina Sienito Brejinho (NSB), alojado em gnaisses do Paleoproterozoico do Complexo Granja. As investigações envolveram mapeamento de detalhe do corpo, acompanhado de análises petrográficas e geocronológicas, que permitiram reconstruir a sua história evolutiva. Foram identificadas cinco fácies petrográficas, com a sua distribuição cartográfica, associações mineralógicas presentes e análises texturais/estruturais sugerindo a atuação de processos de cristalização fracionada, com forte controle da ação da gravidade e imiscibilidade de líquidos na história da cristalização magmática do maciço. Os estudos geocronológicos realizados pelo método Rb-Sr em rocha total revelaram valor de 554 ± 11 Ma, interpretado como a idade mínima para cristalização e emplacement do NSB, no final do Neoproterozoico. No contexto tectônico, esse magmatismo alcalino pode ser relacionado ao evento extensional responsável pela implantação do Gráben Jaibaras e seus correlatos no oeste do Ceará, assim como à granitogênese da região, cujas idades situam-se no intervalo entre 530 e 590 Ma. Situação semelhante é reconhecida na borda norte da Bacia do Amazonas, com o Complexo Alcalino-Ultramáfico-Carbonatítico Maicuru (589 Ma) alojado no embasamento gnáissico paleoproterozoico do Cráton Amazônico. A situação geológica e temporal do NSB permite situá-lo posteriormente à tectônica transcorrente representada na área pela Zona de Cisalhamento Santa Rosa, uma ramificação do Lineamento Transbrasiliano, e anterior à Bacia do Parnaíba. Disso resulta que esse magmatismo alcalino pode ser interpretado como um importante registro da fase rifte que prenunciou a instalação dessa bacia no início do Paleozoico. A sua caracterização, até então sem similar na Província Borborema, abre novas perspectivas de pesquisa em todo o embasamento da Bacia do Parnaíba, tendo em vista a importância tectônica e metalogenética desse tipo de magmatismo.

Magmatism and fenitization in the Cretaceous potassium-alkaline-carbonatitic complex of Ipanema So Paulo State, Brazil

The Ipanema alkaline-carbonatitic complex is part of the Meso-Cenozoic alkaline magmatism located within the southeastern part of the Brazilian Platform. Drill-core and field sampling have indicated the occurrence of glimmerites, with subordinate shonkinites (mela-syenites), clinopyroxene-bearing glimmerites, diorites and syenites. The glimmerites are cross-cut by lamprophyric dykes and calciocarbonatites. Fenitization has deeply affected the country rocks, originating dioritic and syenitic rocks. The Ipanema rocks show a distinct potassic affinity. The initial Sr-Nd- isotopic composition of the Ipanema rocks ((87)Sr/(86)Sr = 0.70661-0.70754 and (143)Nd/(144)Nd = 0.51169-0.51181) is similar to that of tholeiitic and potassium-rich-alkaline rocks of the Eastern Paraguay. Stable isotope data for the Ipanema calciocarbonatite suggest interaction with fluids at temperatures typical of hydrothermal stages, as hypothesized for other carbonatite complexes from southeastern Brazil. The chemical differences between the lamprophyre, glimmerites, carbonatites, apatitites and magnetitites, and the absence of marked REE enrichment in the evolved lithologies, all indicate that fractional crystallization and accumulus of liquidus phases in a magma reservoir, likely coupled with liquid immiscibility processes, may have played an important role in the genesis of the Ipanema rocks.

Sulfide petrology of basalts at DSDP Holes 69-504B and 69-505B

Primary sulfide mineralization in basalts of the Costa Rica Rift occurs mainly in chrome-spinel-bearing olivine tholeiites. Primary sulfides form both globules, consisting of quenched single-phase solid solutions, and irregular polymineralic segregations of pyrrhotite, chalcopyrite, cubanite, and pentlandite. Two types of sulfide solid solutions - iron-nickel (Mss) and iron-copper (Iss) - were found among sulfide globules. These types appear to have formed because of sulfide-sulfide liquid immiscibility in the host magmas; as proved by the presence of globules with a distinct phase boundary between Mss and Iss. Such two-phase globules are associated with large olivine phenocrysts. Inhomogeneties among the globule composition likewise are caused by sulfide-sulfide immiscibility. Secondary sulfides form irregular segregations and veins consisting of pyrite, marcasite, and chalcopyrite.

Chemical composition of glass inclusions of volcanic rocks from the Bonin Arc

The chemical composition of glass inclusions in phenocrystic plagioclase and pyroxene from Sites 792 and 793, drilled during Ocean Drilling Program Leg 126 in the Bonin Arc, is examined. Immiscible liquid, which is preserved as glass inclusions with unmixed textures in plagioclase, is observed in a high-magnesian andesite, which suggests an important role of liquid immiscibility in the fractionation of high-magnesian andesite. In other andesitic rocks (SiO2 = 57-60 wt%), such unmixed textures of glass inclusions in calcic plagioclase with a similar percentage of An (around 80%) is not found. The degree of fractionation and mixing of liquid are inferred from the glass composition in pyroxene.

Activities in liquid Ga-Te alloys at 1120 k

The activity of gallium in liquid Ga-Te alloys has been measured at 1120 K using a solid state galvanic cell incorporating yttria-stabilized thoria as the solid electrolyte. The cell can be schematically represented as (−) W,Re,Ga(1)+Ga2O3(s)|(Y2O3) ThO2|Ga-Te(1) + Ga2O3(s), Re, W (+) The activity of tellurium was derived by Gibbs-Duhem integration. The activity of gallium shows negative deviation from Raoult's law for XGa < 0.6 and positive deviation from ideality for XGa > 0.6. The activity of gallium was constant in the composition range 0.73 < XGa < 0.89, indicating liquid state immiscibility in this region. The Gibbs energy of mixing and the concentration-concentration structure factor at long wavelength limit show a minimum at XGa ≈ 0.4, suggesting strong interactions in the liquid phase with formation of ‘Ga2Te3‘-type complexes

Liquid-liquid phase behavior of toluene/polyethylene oxide/poly(ethyleneoxide-b-dimethylsiloxane) polymer-containing ternary mixtures

The experimental data of phase diagrams for both polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) binary and toluene/polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) ternary polymer-containing systems was obtained at atmosphere pressure by light scattering method. The critical points for some pre-selected compositions and the pressure effect on the phase transition behavior of ternary system were investigated by turbidity measurements. The chosen system is a mixture of ternary which is one of the very few abnormal polymer-containing systems exhibiting pressure-induced both miscibility and immiscibility. This unusual behavior is related to the toluene concentration in the mixtures. The effect of toluene on the phase transition behavior of the ternary polymer-containing mixture was traced. Such behavior can make it possible to process composite materials from incompatible polymers.

Controlling the formation of ionic-liquid-based aqueous biphasic systems by changing the hydrogen-bonding ability of polyethylene glycol end groups

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Binary liquid-liquid equilibria for systems of mono or disubstituted haloakanes (Cl,Br) and pyiridinium based ionic liquids. Advances in the experimentation and interpretation of results

[EN]This work presents the measurements made to define the temperature−composition curves for a set of binary systems composed of several pyridinium-based ionic liquids (ILs) [bpy][BF4] and [bYmpy][BF4] (Y = 2,3,4) with mono- and dihaloalkanes (Cl and Br) in the temperature interval [280−473] K and at atmospheric pressure. With the exception of the short chain dichloroalkanes (1,1- and 1,2-), all the compounds present some degree of immiscibility with the ionic liquids selected.