Phase relationships in the Fe-rich region of the Ce–Nd–B–Fe quaternary system at 773 K

The Fe-rich corner of the Ce–Nd–B–Fe quaternary system at 773 K has been experimentally investigated by means of X-ray powder diffraction and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy techniques. No quaternary compound was observed in this system. Ce2Fe14B and Nd2Fe14B were found to form the continuous solid solution (Ce,Nd)2Fe14B. Ce-Fe4B4 and NdFe4B4 also form the solid solution (Ce,Nd)-Fe4B4. The isothermal section consists of 8 three-phase regions and 2 four-phase regions.

Mechanical Property and Heat Treatment Behaviour of Ti-Zr-Fe Alloys

The element of zirconium (Zr) belongs to the same group 4 as Ti in the periodic table. Therefore it possesses similar chemical properties. The Ti-Zr binary system forms a continuous solid solution for both high temperature β phase with the body centered cubic (BCC) structure and low temperature α phase with the hexagonal close-packed (HCP) structure throughout the entire range of composition. As is well known, on the other hand, the element of iron (Fe) is not only inevitable but also effective element in Ti.By incorporating Fe at the stage of alloy design, off-grade sponge titanium can be employed. Both elements seem to be effective in strengthening the titanium alloys. The purpose of this work was to prepare Ti-Zr-Fe alloys and then mechanical property and heat treatment behaviours were investigated as a fundamental research. Ti-x mass% Zr-1mass% Fe alloys (x=0, 5, 10) were melted in a laboratory-scale arc furnace under a high purity argon atmosphere from the sponge Ti, the sponge Zr and the Fe wire. The resulting ingots were hot forged and rolled at approximately 1120 K to obtain plates of approximately 2 mm in thickness. Well-mixed and homogeneous samples could be obtained, oxygen contaminations were less than 0.09 %. Solid solution of Zr into Ti was confirmed by the XRD peak shift in α phase. Vickers hardness and proof stress increased with Zr content. No remarkable changes could be observed in the microstructures after the solution treatment at 1173 K. However, Young’s modulus increased at x=10 by the treatment.

RESEARCH OF THERMOMETRIC MATERIAL Er1-xScxNiSb. I. MODELLING OF PERFORMANCES

Automated The results of modeling performances of the semiconductor solid solution Er1-xScxNiSb are presented, which can be a promising thermometric material for the manufacture of sensitive elements of thermoelectric and electroresistive thermocouples. Fullprof Suite software was used to model the crystallographic characteristics of the Er1-xScxNiSb thermometric material. Modeling of the electronic structure of Er1-xScxNiSb was performed by Coring-Kon-Rostocker methods in the approximation of coherent potential and local density using the exchange-correlation potential Moruzzi-Janak-Williams and Linear Muffin-Tin Orbital in the framework of DFT density functional theory. The Brillouin zone was divided into 1000 k-points, which were used to model energetic performances by calculating DOS. The width of the energy window was 22 eV and was chosen to capture all semi-core states of p-elements. Full potential (FP) was used in the representation of the linear MT orbital in the representation of plane waves. The accuracy of calculating the position of the Fermi level was εF ± 6 meV. To verify the existence of a continuous solid solution, Er1-xScxNiSb substitution, the change in the values of the period of the unit cell a (x) was calculated within the framework of the DFT density functional theory in the range x = 0–1.0. It is presented that the calculated and experimentally obtained dependences of the period of the unit cell a(x) Er1-xScxNiSb are almost parallel, which confirms the correctness of the used tools and the obtained modeling results. To research the possibility of obtaining thermometric material Er1-xScxNiSb in the form of a continuous solid solution was performed modeling of thermodynamic calculations in the approximation of harmonic oscillations of atoms in the theory of DFT density functional for a hypothetical solid solution Er1-xScxNiSb, x = 0–1.0. It is shown that the change in the values of free energy ΔG(x) (Helmholtz potential) passes through the minimum at the concentration x≈0.1 for all temperatures of possible homogenizing annealing of the samples, indicating the solubility limit of Sc atoms in the structure of the ErNiSb compound. The presence of this minimum indicates that the substitution of Er atoms for Sc atoms in the ErNiSb compound is energetically advantageous only up to the concentration of impurity atoms Sc, x≈0.1. At higher concentrations of Sc atoms, x> 0.10, stratification occurs (spinoidal phase decay). It is shown that modeling of the mixing entropy behavior S even at a hypothetical temperature T = 4000 K shows the absence of complete solubility of Sc atoms in Er1-xScxNiSb. To model the energetic and kinetic performances of the semiconductor thermometric material Er1-xScxNiSb, particularly the behavior of the Fermi level F e , bandgap width g e the distribution of the density of electronic states (DOS) and the behavior of its electrical resistance ρ(x, T) is calculated for an ordered variant of the structure in which the Er atoms in position 4a are replaced by Sc atoms. It is shown that the ErNiSb compound is a semiconductor of the electronic conductivity type, in which the Fermi level is located near the level of the conduction band C e . The modeling showed that at higher concentrations of Sc atoms, the number of generated acceptors exceeds the concentration of uncontrolled donors, and the concentration of free holes exceeds the concentration of electrons. Under these conditions, the Fermi level F e approaches, and then the level of the valence band Er1- xScxNiSb crosses: the dielectric-metal conductivity transition occurs. The experiment should change the sign of the thermo-emf coefficient α(x, T) Er1-xScxNiSb from negative to positive, and the intersection of the Fermi level F e and the valence band changes the conductivity from activating to metallic: on the dependences ln(ρ(1/T)) the activation sites disappear, and the values of resistivity ρ increase with temperature.

Phase relationships in the Ce–Nd–B system at 773 K

Phase relationships in the Ce-Nd-B ternary system at 773 K were investigated by means of X-ray diffraction and scanning electron microscopy with energy dispersive X-ray spectroscopy techniques. Six borides, i. e. CeB4, CeB6, NdB4, NdB6, NdB66 and Nd2B5 are confirmed in this work. No ternary compound was observed. CeB4 and NdB4 were discovered to form the continuous solid solution phase (Ce,Nd)B4, CeB6 and NdB6 also form the solid solution phase (Ce,Nd)B6. The maximum solid solubility of Ce in (Ce,Nd)2B5 phase is 46.5 at.%. The isothermal section of the Ce-Nd-B ternary system at 773 K consists of 3 three-phase regions, 7 two-phase regions and 7 single- phase regions.

Helvine-group minerals from Norwegian granitic pegmatites and some other granitic rocks: Cases of significant Sc and Sn contents

ABSTRACT Helvine-group minerals from two granitic pegmatites have disparate compositions, from nearly pure helvine (Ågskardet, northern Norway; Devonian) to helvine close to ternary compositions (Heftetjern, southern Norway; Precambrian). Metagranite from Høgtuva (northern Norway; Precambrian with Caledonian metamorphic overprint) contains Zn-rich danalite. The Ågskardet helvine contains up to 0.46 wt.% SnO2, and the Heftetjern ternary helvine shows a maximum of 1.74 wt.% Sc2O3. Helvine minerals were also analyzed from three occurrences connected to peralkaline granite (ekerite) of the Permian Oslo Rift. Nearly pure genthelvite (99.19 mol.%) occurs in miarolitic cavities at Gjerdingselva. Two mineralogically different granitic pegmatites derived from the same ekerite pluton in the southern part of the Oslo Rift show quite distinct helvine compositions, from nearly continuous solid solution between helvine and genthelvite in crystals with oscillatory zonation (Rundemyr) to solid solutions midway between danalite and genthelvite (Bakstevalåsen). The Rundemyr crystals have a maximum SnO2 content of 1.28 wt.%. The incorporation of minor elements (Ca, Mg, Al, Sn, Sc) in helvine-group minerals is discussed with emphasis on their chalcophilicity characteristics. For stereochemical reasons, Sn in helvine minerals must be tetravalent, even if Sn2+ is more chalcophile than Sn4+.

Forces generating crystallization differentiation, and the evolution of the melt composition on the example of plagioclase

Crystallization differentiation processes in the melt volume are investigated for albite-anorthite continuous solid solution series. It has shown that crystallization differentiation occurs in the isothermal melt volume due to hydrodynamic instability of the melt/solid particles system. The time of particle settling in a 10 cm thick melt layer is estimated for different particle sizes. In terrestrial conditions, the existence of large melt volumes with long lifetime is possible in the case of a long-lived heat source of high thermal power. This source is a mantle thermochemical plume with a mushroom-shaped head. The particle settling time is estimated for the melt layer thickness, i. e. plume head thickness equal to 10 km. A calculation technique is presented for composition of the melt remaining after settling of plagioclase particles. The results of calculations of changes in the melt composition due to crystallization differentiation at a temperature T = 1410 °C and a pressure P = 6,3 kbar are presented. For a melt whose composition corresponds to N 47,5 (weight percentage of anorthite is 47,5 %), the oxide content in the settled plagioclase, the composition of the melt in its intercrystalline spaces, and the residual melt composition are calculated. At constant temperature, the crystallization differentiation of the melt whose composition corresponds to plagioclase leads to the compositional changes in the initial melt. Calculations of the melt composition have shown that the melt is depleted in anorthite component owing to settling of plagioclase particles. The composition of plagioclase therewith shifts to the liquidus line, reaching its limit on this line

Static compression of Fe4N to 77 GPa and its implications for nitrogen storage in the deep Earth

Compression and decompression experiments on face-centered cubic (fcc) γ′-Fe4N to 77 GPa at room temperature were conducted in a diamond-anvil cell with in situ X-ray diffraction (XRD) to examine its stability under high pressure. In the investigated pressure range, γ′-Fe4N did not show any structural transitions. However, a peak broadening was observed in the XRD patterns above 60 GPa. The obtained pressure-volume data to 60 GPa were fitted to the third-order Birch-Murnaghan equation of state (EoS), which yielded the following elastic parameters: K0 = 169 (6) GPa, K′ = 4.1 (4), with a fixed V0 = 54.95 Å at 1 bar. A quantitative Schreinemakers' web was obtained at 15–60 GPa and 300–1600 K by combining the EoS for γ′-Fe4N with reported phase stability data at low pressures. The web indicates the existence of an invariant point at 41 GPa and 1000 K where γ′-Fe4N, hexagonal closed-packed (hcp) ε-Fe7N3, double hexagonal closed-packed β-Fe7N3, and hcp Fe phases are stable. From the invariant point, a reaction γ′-Fe4N = β-Fe7N3 + hcp Fe originates toward the high-pressure side, which determines the high-pressure stability of γ′-Fe4N at 56 GPa and 300 K. Therefore, the γ′-Fe4N phase observed in the experiments beyond this pressure must be metastable. The obtained results support the existing idea that β-Fe7N3 would be the most nitrogen-rich iron compound under core conditions. An iron carbonitride Fe7(C,N)3 found as a mantle-derived diamond inclusion implies that β-Fe7N3 and Fe7C3 may form a continuous solid solution in the mantle deeper than 1000 km depth. Diamond formation may be related to the presence of fluids in the mantle, and dehydration reactions of high-pressure hydrous phase D might have supplied free fluids in the mantle at depths greater than 1000 km. As such, the existence of Fe7(C,N)3 in diamond can be an indicator of water transportation to the deep mantle.

Topological phases in pyrochlore thallium niobate Tl2Nb2O6+x

The discovery of new topological electronic materials brings a chance to uncover new physics. Up to now, many materials have been theoretically proposed and experimentally proved to host different kinds of topological states. Unfortunately, there is little convincing experimental evidence for the existence of topological oxides. The reason is that oxidation of oxygen leads to ionic crystal in general and makes band inversion unlikely. In addition, the realization of different topological states in a single material is quite difficult, but strongly needed for exploring topological phase transitions. In this work, using first-principles calculations and symmetry analysis, we propose that the experimentally tunable continuous solid solution of oxygen in pyrochlore Tl2Nb2O6+x (0 ≤ x ≤ 1.0) leads to various topological states. Topological insulator, Dirac semimetal, and triply degenerate nodal point semimetal can be realized in it via changing the oxygen content and/or tuning the crystalline symmetries. When x = 1, it is a semimetal with quadratic band touching point at Fermi level. It transits into a Dirac semimetal or a topological insulator depending on the in-plane strain. When x = 0.5, the inversion symmetry is spontaneously broken in Tl2Nb2O6.5, leading to triply degenerate nodal points. When x = 0, Tl2Nb2O6 becomes a trivial insulator with a narrow band gap. These topological phase transitions driven by solid solution of oxygen are unique and physically plausible due to the variation of valence state of Tl+ and Tl3+. This topological oxide will be promising for studying correlation induced topological states and potential applications.