DETERMINATION AND MODELING OF THE LIQUIDUS SURFACE, VAPOR PRESSURE AND IMMISCIBILITY BOUNDARIES IN THE Cu–Pb–S SYSTEM

For the first time using a membrane zero-manometer, the vapor pressure S2 over the surface of the PbS liquidus in the ternary system Cu–Pb–S were determined in the range 1100÷1400 K and 0÷760 mm Hg. Based on the thermodynamic calculation, the boundaries of the immiscibility of liquid alloys of the Cu–S, Pb–S, and Cu–Pb–S systems were determined and analytically described. Critical temperatures and pressures for immiscibility regions of sulfur-rich liquid alloys are characterized by high values: Tcr= 1520÷1880 K; Pcr=170÷510 atm. The crystallization surfaces of lead sulfide with electronic conductivity (p-type PbS) and with hole conductivity (n-type PbS) are calculated and analytically de-scribed, as well as the corresponding values of sulfur vapor pressure over the crystallization surface of lead sulfide. All analytical dependencies for 3D modeling were obtained and visualized using the OriginLab computer program

Phase relations in the CuI-SbSI-SbI3 composition range of the Cu–Sb–S–I quaternary system

The phase equilibria in the Cu-Sb-S-I quaternary system were studied by differential thermal analysis and X-ray phase analysis methods in the CuI-SbSI-SbI3 concentration intervals. The boundary quasi-binary section CuI-SbSI, 2 internal polythermal sections of the phase diagram, as well as, the projection of the liquidus surface were constructed. Primary crystallisation areas of phases, types, and coordinates of non- and monovariant equilibria were determined. Limited areas of solid solutions based on the SbSI (b-phase) and high-temperature modifications of the CuI (α1- and α2- phases) were revealed in the system. The formation of the α1 and α2 phases is accompanied by a decrease in the temperatures of the polymorphic transitions of CuI and the establishment of metatectic (3750C) and eutectoid (2800C) reactions. It was also shown, that the system is characterised by the presence of a wide immiscibility region that covers a significant part of theliquidus surface of the CuI and SbSI based phases

Liquidus surface of the quasi-ternary system Cu2S–In2S3–FeS

A projection of the liquidus surface of the quasi-ternary system Cu2S-In2S3-FeS was constructed as a result of experimental studies of quasi-binary and non-quasi-binary sections and based on the data on binary systems comprising a ternary system.Each section (six quasi-binary and four non-quasi-binary ones) was studied separately using complex methods of physicochemical analysis: differential thermal analysis, X-ray phase analysis, and microstructural analysis.It was found that the quasi-ternary system Cu2S-In2S3-FeS has six fields of primary crystallisation of separate phases and eleven monovariant equilibrium curves along which two phases are co-crystallised. Non-variant equilibrium points were obtained through the extrapolation of the direction of monovariant equilibrium curves.The quasi-ternary system Cu2S-In2S3-FeS is characterised by 17 non-variant equilibrium points, where Е1-Е5 are triple eutectic points.The projection diagram of the liquidus surface is characterised by three crystallisation fields of the initial componets (Cu2S, In2S3, FeS), four fields of binary compounds, and one field of a complex compound (CuFeIn3S6).Since complete solubility of the initial components in liquid and solid states is observed in the quasi-binary section CuIn5S8‑FeIn2S4, the fields of primary crystallisation of CuIn5S8 and FeIn2S4 are absent; they are replaced by an unlimited solid solution based on these components.The fields of primary crystallisation of Cu2S, FeS, and CuInS2 are the most extensive in the ternary system Cu2S-In2S3-FeS. The reactions occurring at monovariant equilibrium points are presented.

Phase relations in the Tl2 Te–TlBiТe2 –TlTbTe2 system

The phase equilibria in the Tl2Te–TlBiТe2–TlTbTe2 concentration area of the Tl–Bi–Tb-Te quaternary system were investigated by using the differential thermal analysis and powder X-ray diffraction techniques. The diagram of the solid-phase equilibria of this system at room temperature was constructed. It was established that the Tl9BiTe6–Tl9TbTe6 section divides the Tl2Te–TlBiТe2–TlTbTe2 system into two independent subsystems. It was found that the Tl2Te–Tl9BiTe6–Tl9TbTe6 subsystem is characterized by the formation of a wide field of solid solutions with a Tl5Te3 structure (δ-phase) that occupy more than 90% of the area of the concentration triangle. The results of X-ray phase analysis of alloys of the Tl9BiTe6–Tl9TbTe6–TlTbTe2–TlBiТe2 subsystem showed the formation of wide regions of solid solutions based on TlTbTe2 and TlBiTe2 along the section of TlTbTe2–TlBiTe2 ((β1- and β2-phases) and made it possible to determine the location of the heterogeneous phase regions in this subsystem. The parameters of crystal lattices of mutually saturated compositions of the β1-, β2-, and δ-phases are calculated from powder diffraction patterns.The paper also presents some polythermal sections, isothermal sections at 740 and 780 K of the phase diagram, as well as projections of the liquidus and solidus surfaces of the Tl2Te–Tl9BiТe6–Tl9TbTe6 subsystem. The liquidus surface consists of three fields of the primary crystallization of α (Tl2Te)-, δ- and β1-phase. The constructed isothermal sections clearly demonstrate that the directions of the tie lines do not coincide with the T–x planes of the studied internal sections, which is characteristic of non-quasi-binary polythermal sections. The obtained new phases are of interest as potential thermoelectric and magnetic materials.

Calculation and evaluation of temperatures and eutectic compositions of multicomponent sections of the CaO—Al2O3—Fe2O3—Cr2O3 system

The predicted service temperatures and eutectic compositions of the polycomponent sections of the CaO—Al2O3—Fe2O3—Cr2O3 system were calculated and evaluated. According to the results of geometrical topological studies of this system, the CaAl2O4—CaFe2O4—CaCr2O4—Ca4Al2Fe2O10 tetrahedron has the largest relative volume and the smallest degree of asymmetry. However, the composition of this tetrahedron includes two compounds that do not have hydraulic activity; this will adversely affect the cement strength. Presence of CaFe2O4 will significantly reduce the composition melting point, that why the CaAl2O4—Ca12Al7O33—CaCr2O4—Ca4Al2F2O10 tetrahedron is of more interest. The calculations result of temperatures and eutectic compositions of triple and tetra-component sections of the CaAl2O4—Ca12Al7O33—CaCr2O4—Ca4Al2F2O10 region of the CaO—Al2O3—Fe2O3—Cr2O3 system are presented. The phases that make up this tetrahedron are highly likely to exist in the CaO—Al2O3—Fe2O3—Cr2O3 system, which will allow us to develop a stable technology for the oil-well cementing materials based on calcium-ferro-alumina chromate cement without special techniques for ensuring high accuracy of the starting components dosage. The paper presents graphic images of the liquidus surface of polycomponent sections of optimal region of system. Selected areas are the most suitable for producing oil-well binding materials with an elevated temperature in application. It was found that, composite materials based on this system can be used at temperatures above 1350 °C. Based on the analysis of temperatures and eutectics compositions of polycomponent section, the use of rational area compositions for producing high-temperature resisting oil-well cement has been proved.

Experimental evidence for decompression melting of metasomatized mantle beneath Colima Graben, Mexico

Primitive subduction zone magmas provide information about the composition and thermal structure of the underlying mantle wedge. In the Colima Graben, Mexico, primitive lavas erupted from cinder cones range from high magnesium calc-alkaline basalts to high-K trachybasalts. This chemical diversity suggests that the sub-arc mantle wedge from which they derive is heterogeneous. To explore the conditions of magma generation in the wedge beneath Colima we used an inverse experimental approach to constrain multiple saturation points on the liquidus surface of a primitive high-K basanite (COM-1). Equilibrium piston-cylinder experiments were carried out between 1.0 and 2.4 GPa under hydrous (1.8–3.8 wt% H2O) and oxidizing (ƒO2 = − 0.5 to 4.3 log units relative to NNO) conditions. COM-1 + 3.8 wt% H2O is shown to be multiply-saturated with a phlogopite-bearing spinel pyroxenite assemblage (cpx + opx + phl + sp) close to its liquidus at 1.9–2.4 GPa and 1300 ºC. Experimental mapping of the liquidus surface reveals a multiple saturation point (MSP) where a lherzolitic phase assemblage of ol + cpx + opx + sp + phl coexist. The topology of the MSP indicates a peritectic of the form cpx + opx + phl + sp = liquid + ol. Four bracketing experiments define the MSP of COM-1 as 1300 ± 10 °C, 1.7 ± 0.1 GPa, ∆NNO = 3.4 ± 0.5 log units, for melt containing 3.6 ± 0.4 wt% H2O. The MSP olivine is too forsterite-rich (Fo92-94) to be in equilibrium with mantle lherzolite, but matches phenocryst core compositions in the natural basanite. Thus, experimental results indicate that COM-1 was produced by incongruent melting of an olivine-free, phlogopite-pyroxenite source that itself is the result of metasomatism of mantle wedge by slab-derived fluids. These conditions provide a valuable constraint on the thermal structure and chemical composition of the mantle wedge beneath Colima.

Thermal Analysis of High Entropy Rare Earth Oxides

Phase transformations in multicomponent rare earth sesquioxides were studied by splat quenching from the melt, high temperature differential thermal analysis and synchrotron X-ray diffraction on laser-heated samples. Three compositions were prepared by the solution combustion method: (La,Sm,Dy,Er,RE)2O3, where all oxides are in equimolar ratios and RE is Nd or Gd or Y. After annealing at 800 °C, all powders contained mainly a phase of C-type bixbyite structure. After laser melting, all samples were quenched in a single-phase monoclinic B-type structure. Thermal analysis indicated three reversible phase transitions in the range 1900–2400 °C, assigned as transformations into A, H, and X rare earth sesquioxides structure types. Unit cell volumes and volume changes on C-B, B-A, and H-X transformations were measured by X-ray diffraction and consistent with the trend in pure rare earth sesquioxides. The formation of single-phase solid solutions was predicted by Calphad calculations. The melting point was determined for the (La,Sm,Dy,Er,Nd)2O3 sample as 2456 ± 12 °C, which is higher than for any of constituent oxides. An increase in melting temperature is probably related to nonideal mixing in the solid and/or the melt and prompts future investigation of the liquidus surface in Sm2O3-Dy2O3, Sm2O3-Er2O3, and Dy2O3-Er2O3 systems.

High-pressure silica phase transitions: Implications for deep mantle dynamics and silica crystallization in the protocore

The subsolidus phase diagram of silica in the 80–220 GPa pressure range was determined by density functional theory (DFT). The transition pressures calculated using the generalized gradient approximation (GGA) in the static limit (at 0 K, without zero point vibrational energy) for the β-stishovite (CaCl2-structure) to seifertite and the seifertite to pyrite-type transitions are 95 and 213 GPa, respectively. These are in good agreement with those calculated using hybrid functionals, giving transition pressures of 96 and 215 GPa. This indicates that previous local density approximation (LDA) results underestimate the transition pressure by 10–15 GPa. Density functional perturbation theory calculations, carried out using GGA within the quasi-harmonic approximations, give Clapeyron slopes of 5.4 and −2.8 MPa/K for the β-stishovite to seifertite and seifertite to pyrite-type transitions, respectively. This suggests that the seifertite-forming transition occurs at 109 GPa (470 km above the core-mantle boundary, CMB) at an ambient mantle geotherm, whereas the pyrite-type transition occurs at 200 GPa (620 km below the CMB) at 4700 K, which is close to the core adiabat. We also calculate the equation of state and show that the stability of seifertite in the lowermost mantle contributes negative buoyancy to recycled oceanic crust, although not as much as in some previous studies. Nevertheless, the increased density of seifertite over β-stishovite may lead to layers with elevated proportions of basaltic material within the large low S-wave velocity provinces. The seifertite to pyrite-type silica transition in the outer core will affect the silica liquidus surface in the system Fe-Si-O and forms a basis for further investigations of silica crystallization in the protocore.