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Crystal structure and low-energy Einstein mode in ErV{sub 2}Al{sub 20} intermetallic cage compound

Single crystals of a new ternary aluminide ErV{sub 2}Al{sub 20} were grown using a self-flux method. The crystal structure was determined by powder X-ray diffraction measurements and Rietveld refinement, and physical properties were studied by means of electrical resistivity, magnetic susceptibility and specific heat measurements. These measurements reveal that ErV{sub 2}Al{sub 20} is a Curie-Weiss paramagnet down to 1.95 K with an effective magnetic moment μ{sub eff} =9.27(1) μ{sub B} and Curie-Weiss temperature Θ{sub CW} =−0.55(4) K. The heat capacity measurements show a broad anomaly at low temperatures that is attributed to the presence of a low-energy Einstein mode with characteristic temperature Θ{sub E} =44 K, approximately twice as high as in the isostructural ‘Einstein solid’ VAl{sub 10.1}. - Graphical abstract: A low-energy Einstein mode is observed in a novel intermetallic cage compound ErV{sub 2}Al{sub 20} by specific heat and resistivity measurements. - Highlights: • Single crystals of a new compound ErV{sub 2}Al{sub 20} were grown by self-flux method. • Crystal structure is reported, based on powder x-ray diffraction. • ErV{sub 2}Al{sub 20} is a Curie-Weiss paramagnet. • Low-energy ‘rattling’ phonon mode (Θ{sub E}=44 K) is found in specific heat measurements.

36 MATERIALS SCIENCE↗

Method of manufacturing superconductor wire

A method for forming Nb.sub.3Sn superconducting wire is provided. The method employs a powder-in-tube process using a high-tin intermetallic compound, such as MnSn.sub.2, for producing the Nb.sub.3Sn. The use of a high-tin intermetallic compound enables the process to perform hot extrusion without melting the high-tin intermetallic compound. Alternatively, the method may entail drawing the wire without hot extrusion.

36 MATERIALS SCIENCE↗

Electrochemical behavior of Nd and its co-reduction with Bi in molten LiCl-KCl salts - 18360

A molten salt phase is used as the solvent in pyrochemical reprocessing. The molten salt waste generated in pyro-processes contains the residual lanthanides and actinides as various compounds. Various methods have been proposed for recovering and recycling these useful elements. The separation of actinides from lanthanides is performed by electrolysis or reductive extraction. Herein we have studied PyroRedSox-based co-reduction of Nd and Bi via electrolysis in a molten chloride salt. The redox behavior of Nd and the formation potential of intermetallic compounds of Nd and Bi were determined using cyclic voltammetry (CV). Electrorefining was performed under a constant reductive potential at 773 K in LiCl-KCl eutectic mixture; the co-reduction potential was -1.37 V. Lastly, the co-reduction potential of the intermetallic compound was applied to reduce the amount of Nd and Bi. Scanning electron microscopy (SEM) revealed that various kinds of intermetallic compounds were formed in Bi and Nd, and were deposed in the lower part of the molten salt, allowing purification of the contaminated molten salt. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High-temperature studies of the magnetic susceptibility of samarium and the Al{sub 2}Sm compound

The magnetic susceptibility of metallic samarium and the Al{sub 2}Sm intermetallic compound has been experimentally studied by the Faraday method in the temperature range of 300-1800 K. It has been shown that the temperature dependences of the magnetic susceptibility of Sm and Al{sub 2}Sm in a crystalline state can be described in the framework of Van Vleck paramagnetism theory taking into account variable valence and the contribution from the conduction electrons. Using this theoretical interpretation of the data, the effective valence of samarium in the metallic state and in the Al{sub 2}Sm intermetallic compound has been estimated as a function of the temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermal Calculations to Determine Maximum Zircaloy Temperatures During Reactor Operations for Campaign 1 Fuel Assemblies

The H-Canyon Facility plans on processing bundles from Non-Aluminum Spent Nuclear Fuel (NASNF) Risk Group 1 (UO 2 core fuels). Uranium-zirconium (UZr) alloys and zirconium clad UO 2 fuel containing UZr intermetallic compound have the potential to cause explosions during dissolution. UZr intermetallic typically only forms when uranium and zirconium (or zirconium alloy) cladding are in contact at high temperatures. Thermal modeling was performed to determine the maximum cladding temperature for Campaign 1 Zircoloy cladded fuel assembles during reactor operation to help determine if the UZr intermetallic compound could have formed during reactor operations. The temperature of 350°C was chosen as a conservative minimum value for the possible formation of intermetallic UZr compound. The modeling approach, inputs, and results are outlined in this document.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructure and mechanical properties of diffusion bonded W/steel joint using V/Ni composite interlayer

Diffusion bonding between W and steel using V/Ni composite interlayer was carried out in vacuum at 1050 °C and 10 MPa for 1 h. The microstructural examination and mechanical property evaluation of the joints show that the bonding of W to steel was successful. No intermetallic compound was observed at the steel/Ni and V/W interfaces for the joints bonded. The electron probe microanalysis and X-ray diffraction analysis revealed that Ni{sub 3}V, Ni{sub 2}V, Ni{sub 2}V{sub 3} and NiV{sub 3} were formed at the Ni/V interface. The tensile strength of about 362 MPa was obtained for as-bonded W/steel joint and the failure occurred at W near the V/W interface. The nano-indentation test across the joining interfaces demonstrated the effect of solid solution strengthening and intermetallic compound formation in the diffusion zone. - Highlights: • Diffusion bonding of W to steel was realized using V/Ni composite interlayer. • The interfacial microstructure of the joint was clarified. • Several V–Ni intermetallic compounds were formed in the interface region. • The application of V/Ni composite interlayer improved the joining quality.

36 MATERIALS SCIENCE↗

Magnetic properties and transformation of crystal structure in the ErFe{sub 2}-ErAl{sub 2} system

The modification of structural properties and magnetic behaviour of the ErFe{sub 2−x}Al{sub x} Laves phase intermetallic compounds have been studied while changing the Al content in the range 0.36 ≤ x ≤ 1.5. Powder X-ray diffraction study at room temperature showed the formation of the cubic C15 structure, in the samples with Al content of 0.36 ≤ x < 0.75 and 1.4 ≤ x ≤ 2.0. For the intermediate compositions with 0.75 ≤ x ≤ 1.4, the hexagonal C14 structure is observed. Magnetic and magnetocaloric properties of polycrystalline ErFe{sub 2−x}Al{sub x} intermetallic compounds were investigated experimentally using magnetic and heat capacity measurements. The Curie temperature T{sub C} decreases from 275 to 28 K as the Al content increases from x = 0.36 to x = 1.5, respectively. Magnetization measurements in strong magnetic fields showed the complex mechanism of magnetic saturation in the studied compounds. Under an external field change from 0 to 2 T, the maximum entropy change is 6 J/kg K at T = 28 K for the composition with x = 1.5. The minimum in the concentration dependence of the magnetic entropy change is observed in the vicinity of x equal to 1.25. Regularities of variations of magnetocaloric properties of ErFe{sub 2−x}Al{sub x} intermetallic compounds with increasing Al content are discussed from the point of view of their both structural and magnetic states.

36 MATERIALS SCIENCE↗

The study of the structure of the electronic states of the FeGa{sub 3} and RuGa{sub 3} compounds by optical spectroscopy method

Investigations of the optical properties of intermetallic compounds FeGa{sub 3} and RuGa{sub 3} in the wavelength range of 0.22−14 μm have been conducted. The spectra of the interband light absorption are interpreted based on comparative analysis of calculated and experimental dispersion dependences of optical conductivity. Experimental data confirm the existence of the energy gaps at the Fermi level with a width of ~0.6 eV in the density of states of these materials, which was previously predicted in the band calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermodynamic characteristics of praseodymium in the gallium–aluminum eutectic melt

The Ga–Al eutectic melt saturated with praseodymium was studied in the temperature range 572–1076 K by electromotive force (emf) method relative to the reference electrode (In{sub L} + PrIn{sub 3}, where L is the liquid phase) in a LiCl–KCl–CsCl eutectic electrolyte. The partial molar thermodynamic functions (enthalpy, entropy, and Gibbs energy) of praseo dymium in a Ga–Al eutectic melt were calculated. According to the emf measurements of the two-phase Pr–Ga–Al{sub L} + intermetallic compound alloys equilibrated with the Ga–Al eutectic melt saturated with praseodymium, there are intermetallic compounds PrGa{sub 6}, PrGa{sub 4}, and Pr{sub 0.22}Ga{sub 0.78}(PrGa{sub 2}) in the temperature ranges 572–741, 741–883, and 883–1076 K, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extending the applicability of the Tkatchenko-Scheffler dispersion correction via iterative Hirshfeld partitioning

Recently we have demonstrated that the applicability of the Tkatchenko-Scheffler (TS) method for calculating dispersion corrections to density-functional theory can be extended to ionic systems if the Hirshfeld method for estimating effective volumes and charges of atoms in molecules or solids (AIM’s) is replaced by its iterative variant [T. Bučko, S. Lebègue, J. Hafner, and J. Ángyán, J. Chem. Theory Comput. 9, 4293 (2013)]. The standard Hirshfeld method uses neutral atoms as a reference, whereas in the iterative Hirshfeld (HI) scheme the fractionally charged atomic reference states are determined self-consistently. We show that the HI method predicts more realistic AIM charges and that the TS/HI approach leads to polarizabilities and C{sub 6} dispersion coefficients in ionic or partially ionic systems which are, as expected, larger for anions than for cations (in contrast to the conventional TS method). For crystalline materials, the new algorithm predicts polarizabilities per unit cell in better agreement with the values derived from the Clausius-Mosotti equation. The applicability of the TS/HI method has been tested for a wide variety of molecular and solid-state systems. It is demonstrated that for systems dominated by covalent interactions and/or dispersion forces the TS/HI method leads to the same results as the conventional TS approach. The difference between the TS/HI and TS approaches increases with increasing ionicity. A detailed comparison is presented for isoelectronic series of octet compounds, layered crystals, complex intermetallic compounds, and hydrides, and for crystals built of molecules or containing molecular anions. It is demonstrated that only the TS/HI method leads to accurate results for systems where both electrostatic and dispersion interactions are important, as illustrated for Li-intercalated graphite and for molecular adsorption on the surfaces in ionic solids and in the cavities of zeolites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Strength, Superelastic Compounds

In a previous disclosure, the use of 60- NiTiNOL, an ordered intermetallic compound composed of 60 weight percent nickel and 40 weight percent titanium, was investigated as a material for advanced aerospace bearings due to its unique combination of physical properties. Lessons learned during the development of applications for this material have led to the discovery that, with the addition of a ternary element, the resulting material can be thermally processed at a lower temperature to attain the same desirable hardness level as the original material. Processing at a lower temperature is beneficial, not only because it reduces processing costs from energy consumption, but because it also significantly reduces the possibility of quench cracking and thermal distortion, which have been problematic with the original material. A family of ternary substitutions has been identified, including Hf and Zr in various atomic percentages with varying concentrations of Ni and Ti. In the present innovation, a ternary intermetallic compound consisting of 57.6 weight percent Ni, 39.2 weight percent Ti, and 3.2 weight percent Hf (54Ni-45Ti-1Hf atomic percent) was prepared by casting. In this material, Hf substitutes for some of the Ti atoms in the material. In an alternate embodiment of the innovation, Zr, which is close in chemical behavior to Hf, is used as the substitutional element. With either substitution, the solvus temperature of the material is reduced, and lower temperatures can be used to obtain the necessary hardness values. The advantages of this innovation include the ability to solution-treat the material at a lower temperature and still achieve the required hardness for bearings (at least 50 Rockwell C) and superelastic behavior with recoverable strains greater than 2%. Most structural alloys will not return to their original shape after being deformed as little as 0.2% (a tenth of that possible with superelastic materials like 60 NiTiNOL). Because lower temperatures can be used in the heat treatment process, less energy will be consumed, and there will be less dimensional distortion and quench cracking. This results in fewer scrap parts, less material waste from large amounts of material removal, and fewer machining steps to rework parts that are out of specification. This material has a combination of properties that have been previously unobtainable. The material has a Young s modulus of approximately 95 GPa (about half that of conventional steels), moderate density (10 to 15% lower than conventional steels), excellent corrosion resistance, and high hardness (58 to 62 HRC). These properties make this material uniquely suited for advanced bearings.

Stanford, Malcolm↗

Titanium-deposition assisted brazing of SiC ceramics using inactive AgCu filler

Highlights: • Reliable joint of SiC ceramics was achieved via Titanium-deposition assisted brazing using inactive AgCu filler metal. • Microstructure characteristic of deposited-SiC brazed joint was investigated in detail. • Ti-deposition assisted brazing inhibited the formation of numerous intermetallic compounds. - Abstract: In this study, active titanium element film was designed to deposit on SiC ceramics directly to enhance the brazability of inactive AgCu brazing alloy on ceramics. The result showed the reliable joint was successfully obtained and the deposition of titanium film on SiC directly inhibited the formation of amounts of intermetallic compounds effectively in the brazing seam. Detailed interfacial microstructure of joint investigated by scanning electron microscope equipped with energy dispersive spectrum analysis and transmission electron microscope revealed that the interfacial reactions were based on deposited Ti film. The typical joint was SiC/TiCu + Ti{sub 2}Cu/TiC/Ti{sub 5}Si{sub 3} containing TiC particles/Ag(s,s) + Cu(s,s)/Ti{sub 5}Si{sub 3} containing TiC particles/TiC/TiCu + Ti{sub 2}Cu/SiC.

36 MATERIALS SCIENCE↗

The Effects of Grain Refinement and Rare Earth Intermetallics on Mechanical Properties of As-Cast and Wrought Magnesium Alloys

The effects of rare earth intermetallics and grain refinement by alloying and hot extrusion on the mechanical properties of Mg-Gd-Al-Zn alloys have been studied to elucidate some useful ways to enhance the mechanical properties of magnesium alloys. It was revealed that aluminum as an alloying element is a much better grain refining agent compared with gadolinium, but the simultaneous presence of Al and Gd can refine the as-cast grain size more efficiently. The presence of fine and widely dispersed rare earth intermetallics was found to be favorable to achieve finer recrystallized grains during hot deformation by extrusion. The presence of coarse dendritic structure in the GZ61 alloy, grain boundary eutectic containing Mg{sub 17}Al{sub 12} phase in the AZ61 alloy, and rare earth intermetallics with unfavorable morphology in the Mg-4Gd-2Al-1Zn alloy was found to be detrimental to mechanical properties of the alloy in the as-cast condition. As a result, the microstructural refinement induced by hot extrusion process resulted in a significant enhancement in strength and ductility of the alloys. The presence of intermetallic compounds in the extruded Mg-4Gd-2Al-1Zn and Mg-2Gd-4Al-1Zn alloys deteriorated tensile properties, which was related to the fact that such intermetallic compounds act as stress risers and microvoid initiation sites.

36 MATERIALS SCIENCE↗

The Influence of Nickel Additions to Liquid A359 on Hot-Dip Aluminizing of Solid S45C Steel

The properties of hot-dipping A359 aluminum alloys can be improved by strategically placing the S45C steel inserts to locally improve properties such as oxidation and corrosion resistance, but soft A359 aluminum alloy can be easily worn out and thus decreased the S45C steel’s reliability. In this study, we have been added 20 wt.%Ni to increases the hardness of the A359 aluminum alloy, then hot dipped the S45C steel into the molten A359-20 wt.%Ni aluminum alloy for 1 min and then heat treated at 400-600 °C. The effect of nickel on the interface characteristic (including kinetic and shear strengths of interface between the S45C steel and aluminum alloy) and the surface glossiness and wear property of the A359-Ni aluminum alloy is also discussed. The experimental results show that the Fe{sub 2}Al{sub 5} intermetallic compound thus the activation energy of the compound formation in the A359-20 wt.%Ni aluminum alloy, and its thickness increased with an increase in heating temperature. Nickel hindered formation of the Fe{sub 2}Al{sub 5} intermetallic compound thus the activation energy of the compound formation in the A359-20 wt.%Ni aluminum alloy (0.413 eV) is larger than A359 aluminum alloy. The nickel could increase the surface glossiness and anti-wear of the hot-dipped coating layer, but they would not deteriorate the interface shear strength.

36 MATERIALS SCIENCE↗

Study of morphology and magnetic properties of the HoNi{sub 3} crystalline and ball-milled compound

The morphology and magnetic properties of the HoNi{sub 3} crystalline and ball-milled intermetallic compounds are presented. The polycrystalline HoNi{sub 3} bulk compound crystallizes in the rhombohedral PuNi{sub 3} — type of crystal structure and indicates ferrimagnetic arrangement with the Curie temperature of T{sub C} = 57 ± 2 K, the helimagnetic temperature T{sub h} = 23 ± 2 K with the total saturation magnetic moment of 6.84 μ{sub B}/f.u. at 2 K. The use of the ball-milling method leads to the formation of HoNi{sub 3} nanoflakes with typical thickness of less than 100 nm prone to agglomeration upon milling. The increase of grinding duration leads to the reduction in crystallite size, which was confirmed by various complementary microscopical and diffraction studies. Moreover, the increase in milling duration results in the emergence of the relatively small coercivity (H{sub C}), remanence (M{sub r}) and a variation of the saturation magnetization (M{sub S}). - Graphical abstract: Display Omitted - Highlights: • The ball-milling method exhibits significant potential for producing RT{sub 3} nanopowders. • The AFM method was used for the first time in analysis of R–T nanoflakes morphology. • HoNi{sub 3} compound forms polycrystalline and textured nanoflakes evolving upon milling. • The decrease in crystallite size via grinding is confirmed by XRD, TEM and AFM. • The magnetic parameters were sensitive to the extension of pulverization b.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Phase equilibria, formation, crystal and electronic structure of ternary compounds in Ti-Ni-Sn and Ti-Ni-Sb ternary systems

The phase equilibria of the Ti-Ni-Sn and Ti-Ni-Sb ternary systems have been studied in the whole concentration range by means of X-ray and EPM analyses at 1073 K and 873 K, respectively. Four ternary intermetallic compounds TiNiSn (MgAgAs-type), TiNi{sub 2-x}Sn (MnCu{sub 2}Al-type), Ti{sub 2}Ni{sub 2}Sn (U{sub 2}Pt{sub 2}Sn-type), and Ti{sub 5}NiSn{sub 3} (Hf{sub 5}CuSn{sub 3}-type) are formed in Ti-Ni-Sn system at 1073 K. The TiNi{sub 2}Sn stannide is characterized by homogeneity in the range of 50-47 at% of Ni. The Ti-Ni-Sb ternary system at 873 K is characterized by formation of three ternary intermetallic compounds, Ti{sub 0.8}NiSb (MgAgAs-type), Ti{sub 5}Ni{sub 0.45}Sb{sub 2.55} (W{sub 5}Si{sub 3}-type), and Ti{sub 5}NiSb{sub 3} (Hf{sub 5}CuSn{sub 3}-type). The solubility of Ni in Ti{sub 0.8}NiSb decreases number of vacancies in Ti site up to Ti{sub 0.91}Ni{sub 1.1}Sb composition. - Graphical abstract: Isothermal section of the Ti-Ni-Sn phase diagram and DOS distribution in hypothetical TiNi{sub 1+x}Sn solid solution. Highlights: Black-Right-Pointing-Pointer Ti-Ni-Sn phase diagram was constructed at 1073 K. Black-Right-Pointing-Pointer Four ternary compounds are formed: TiNiSn, TiNi{sub 2-x}Sn, Ti{sub 2}Ni{sub 2}Sn, and Ti{sub 5}NiSn{sub 3}. Black-Right-Pointing-Pointer Three ternary compounds exist in Ti-Ni-Sb system at 873 K. Black-Right-Pointing-Pointer The TiNi{sub 2}Sb compound is absent.

36 MATERIALS SCIENCE↗

Effect of Cu Interlayer on the Microstructure and Strength for Brazing of Tungsten/316L Steel

Brazing is an effective technique for joining tungsten and steel. However, the high residual stresses are produced due to the different coefficients of thermal expansions between tungsten and steel. Compared with the direct brazing with BNi-2 foil filler, BNi-2/Cu/ BNi-2 multiple interlayer was used as filler to minimize the residual stresses between tungsten and 316L steel. The brazing experiments were conducted at 1050 °C for 25 min using Cu foils with different thickness. The results show that tungsten and 316L steel have been successfully joined by brazing. The intermetallic compound of NiW formed at the W/BNi-2 interface, which was detrimental to the strength of the joint. The microhardness of different diffusion zones is higher than that of the substrates owing to the formation of intermetallic compound and solid solution. All specimens of shear testing fractured at the W/BNi-2 interface close to W substrate, and the average strength of joints was 197, 275 and 268 MPa with multiple interlayer thickness of 0.2 , 0.1 and 0.05 mm copper foil, respectively, while the average strength of joints was 143 MPa with BNi-2 foil filler. The significant increase in the joint shear strength can be ascribed to the Cu foil in the multiple interlayer because of with excellent plasticity and toughness.

36 MATERIALS SCIENCE↗

Phase constitution in the interfacial region of laser penetration brazed magnesium–steel joints

The phase constitution in the interfacial region of laser penetration brazed magnesium–steel joints was investigated using electron microscopy. From the distribution of elements, the transition zone was mainly composed of elements Mg and Fe along with some Al and O. Furthermore, the transition layer consisted mainly of intermetallic compounds and metal oxides. The compounds were identified as Al-rich phases, such as Mg{sub 17}Al{sub 12}, Mg{sub 2}Al{sub 3}, FeAl and Fe{sub 4}Al{sub 13}. More noteworthy was that the thickness of the transition layer was determined by Fe–Al compounds. The presence of FeAl and Fe{sub 4}Al{sub 13} was a result of the complex processes that were associated with the interfacial reaction of solid steel and liquid Mg–Al alloy. - Highlights: • A technology of laser penetration brazed Mg alloy and steel has been developed. • The interface of Mg/Fe dissimilar joints was investigated using electron microscopy. • The transition layer consisted of intermetallic compounds and metal oxides. • Moreover, the thickness of transition layer was determined by Fe/Al compounds. • The presence of FeAl and Fe{sub 4}Al{sub 13} was associated with the interfacial reaction.

36 MATERIALS SCIENCE↗