Enthalpies of formation of selected Pd2YZ Heusler compounds

Standard enthalpies of formation of selected ternary Pd-based Heusler type compositions Pd₂YZ (Y = Cu, Hf, Mn, Ti, Zr; Z = Al, Ga, In, Ge, Sn) were measured using high temperature direct synthesis calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the Heusler compounds are, Pd₂HfAl (−81.6 ± 2.4); Pd₂HfGa (−79.9 ± 2.9); Pd₂HfIn (−76.4 ± 1.4); Pd₂HfSn (−77.6 ± 1.6); Pd₂MnSn (−54.6 ± 3.1); Pd₂TiGa (−65.6 ± 3.6); Pd₂TiIn (−69.9 ± 2.1); Pd₂TiSn (−78.6 ± 2.4); Pd₂ZrAl (−85.3 ± 3.0); Pd₂ZrGa (−76.2 ± 1.9); Pd₂ZrIn (−85.1 ± 3.9); Pd₂ZrSn (−92.2 ± 3.1); for the B2 compounds, Pd₂MnAl (−87.1 ± 3.0); Pd₂MnGa (−54.5 ± 1.7); Pd₂MnIn (−41.0 ± 2.5); Pd₂TiAl (−81.4 ± 1.9); for the tetragonal compound Pd₂CuAl (−55.2 ± 3.0) and for the orthorhombic compound Pd₂CuSn (−43.1 ± 2.3). Values were compared with those from published first principles calculation and the Open Quantum Materials Database (OQMD). Lattice parameters of these compounds were determined by X-ray diffraction analysis (XRD). Microstructures were identified using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Selected alloys were annealed at various temperatures to investigate phase transformations and phase relationships.     

Strong coupling effects during Cu/In/Ni interfacial reactions at 280 °C

The substantial heat generated in three-dimensional integrated circuits and high-power electronics has made thermal management a critical challenge for reliability in the electronics industry. Pure indium solder has been used as a thermal interface material to minimize the contact thermal resistance between a chip and its heat sink. Indium and indium-based alloys are potential lead-free solder for low-temperature applications. Heat sinks in the heat dissipation system as well as substrates of electronic joints are usually made of copper, with nickel being the most commonly used diffusion barrier on the chip side. Therefore, the Cu/In/Ni sandwich structure would be encountered in electronic devices. The soldering process for forming the Cu/In/Ni structure crucially determines the reliability of devices. In this study, Cu/In/Ni interfacial reactions at 280 °C were investigated. Intermetallic compounds were identified and the microstructural evolution was observed. A strong coupling effect between Cu and Ni was found, which caused several peculiar phenomena: (1) the formation of a Cu–In compound (the Cu₁₁In₉ phase) at the In/Ni interface; (2) the formation of two sub-layers of the Cu₁₁In₉ phase at the Cu/In interface; (3) the formation of faceted rod-like Cu₁₁In₉ grains; and (4) the formation of a half-Cu₁₁In₉, half-Ni₃In₇ microstructure after prolonged reactions. The mechanism of phase transformations is elucidated based on the calculated Cu–In–Ni ternary phase diagram using CALPHAD thermodynamic modeling.     

Phase equilibria in the Fe–Al–Nb system: Solidification behaviour,liquidus surface and isothermal sections

The Fe–Al–Nb phase diagram including isothermal sections at 1000, 1150, and 1300 °C as well as the liquidus surface and corresponding reaction scheme was studied experimentally by a combination of scanning electron microscopy (SEM), electron probe microanalysis (EPMA), X-ray diffraction (XRD), and differential thermal analysis (DTA). No genuinely ternary intermetallic phase exists in the system, but the two Fe–Nb phases NbFe₂ (C14-type Laves phase) and Fe₇Nb₆ (μ phase) have extended homogeneity ranges in the ternary system, where large amounts of Fe can be substituted by Al in both cases. The solubility of the third element was studied for all binary phases and the effect on the lattice parameters is discussed. From analysis of the as-cast microstructures and DTA experiments, the liquidus surface including all invariant reactions as well as the occurring solid state reactions were established. Three ternary eutectics, one eutectoid, and two peritectic reactions were found, and the list of invariant points is completed by seven U-type reactions.     

Liquid-state interfacial reactions in Sn–Zn/Pd couples and phase equilibria of the Sn–Zn–Pd system at 260 °C

This study investigated the effects of Zn contents on the reaction products and microstructural evolution in the liquid/solid Sn–Zn/Pd interfacial reactions at 260 °C. A uniform Pd₂Zn₉ layer was formed at the Sn–9 wt.%Zn/Pd interface. The reaction phase transited from Pd₂Zn₉ to PdSn₄ when the Zn content decreased from 2 wt.% to 1 wt.%. The most striking feature is that the PdSn₄ growth was greatly suppressed with only 0.5 wt.% Zn addition in solders. Additionally, a drastic microstructural evolution was observed in the Sn–1.5 wt.%Zn/Pd reaction. The Pd₂Zn₉ layer was initially formed and then it was detached from the interface due to the decrease in the Zn content. Subsequently, the dominant phase changed to the PdSn₄ phase. Furthermore, a partial isothermal section in the Sn–Zn–Pd ternary system (less than 20 at.%Pd) at 260 °C was experimentally determined. The liquid apex of the liquid + PdSn₄ + Pd₂Zn₉ tie-triangle was located at Sn–2.7 at.%Zn–1.0 at.%Pd. The phase transition from Pd₂Zn₉ to PdSn₄ in the interfacial reactions was in good agreement with the phase equilibria relationship.     

Thermal conductivity of Ni3V–Ni3Al pseudo-binary alloys

The effect of changes in the composition and microstructure of the Ni₃V–Ni₃Al pseudo-binary alloys on their thermal conductivity has been investigated. For Ni₃V and Ni₃Al-based single-phase alloys, the thermal conductivity shows a maximum value at the stoichiometric compositions, and it decreases as the V (or Al) content of the Ni₃Al (or Ni₃V) alloy increases, following the Nordheim rule. For Ni₃V–Ni₃Al two-phase alloys, the thermal conductivity of the constituent Ni₃Al phase exhibits a smaller value than that of the Ni₃V phase. Eventually, the thermal conductivity of the two-phase alloys decreases as the Al content increases because of the increase in the volume fraction of the Ni₃Al phase with low conductivity. As the temperature increases from 293 K to 1073 K, the conductivity increases for all of the alloys but not for stoichiometric Ni₃V. However, the dependence of the thermal conductivity on the alloy composition between 293 K and 1073 K is similar. Hence, it is confirmed that the thermal conductivity of the Ni₃V–Ni₃Al pseudo-binary alloys is controlled by the composition and volume fraction of the constituent phase.     

Solidification morphology and phase selection in drop-tube processed Ni–Fe–Si intermetallics

Drop-tube processing was used to rapidly solidify droplets of Ni_64.7Fe₁₀Si_25.3 and Ni_59.7Fe₁₅Si_25.3 alloys. In the larger droplets, and therefore at low cooling rates, only two phases, γ-Ni₃₁Si₁₂ and β₁-Ni₃Si were observed. Conversely, in the smaller droplets, and therefore at higher cooling rates, the metastable phase Ni₂₅Si₉ was also observed. The critical cooling rate for the formation of Ni₂₅Si₉ was estimated as 5 × 10³ K s⁻¹. SEM and TEM analysis reveals three typical microstructures: (I) a regular structure, comprising single-phase γ-Ni₃₁Si₁₂ and a eutectic structure between γ-Ni₃₁Si₁₂ and β₁-Ni₃Si; (II) a refined lamellar structure with a lamellar spacing <50 nm comprising γ-Ni₃₁Si₁₂ and β₁-Ni₃Si; (III) an anomalous structure with a matrix of Ni₂₅Si₉ and only a very small proportion of a second, and as yet unidentified, phase. These results indicate that there is an extended stability field for Ni₂₅Si₉ in the Ni-rich part of the Ni–Fe–Si ternary system in comparison to the Ni–Si binary system. With an increase of cooling rate, an increasing fraction of small droplets experience high undercoolings and, therefore, can be undercooled into the Ni₂₅Si₉ stability field forming droplets consisting of only the anomalous structure (III). The Fe atoms are found to occupy different substitutional sites in different phase, i.e. Fe substitutes for Ni in the γ phase and Si in the L1₂ (β₁) phase respectively.     

First-principles density functional calculations of physical properties of orthorhombic Au2Al crystal

The study attempts to perform a systematical investigation of the thermodynamic, mechanical and electronic properties of orthorhombic Au₂Al crystal by using first-principles calculations incorporated with a quasi-harmonic Debye model. In addition, their temperature, hydrostatic pressure and direction dependences are also addressed. The investigation begins with evaluation of the equilibrated lattice constants and elastic constants of Au₂Al single crystal. Next, the mechanical features of the single crystal, such as ductile-brittle characteristic and elastic anisotropy, are assessed based on the Cauchy pressures, shear anisotropy factors and directional Young's modulus. Alternatively, the pressure-dependence of polycrystalline mechanical properties of Au₂Al, including bulk, shear and Young's moduli, and ductility, brittleness and microhardness characteristics are also estimated. Furthermore, the study also characterizes the temperature-dependence of thermodynamic properties of Au₂Al single crystal, namely, Debye temperature and heat capacity. At last, electronic characteristic analysis is carried out to predict the electronic band structures and density of states profiles of the crystal.The calculation results indicate that Au₂Al crystal is an elastically anisotropic material at zero pressure and a highly ductile material with low stiffness. In addition, the Young's moduli of the crystal would be markedly enhanced with the increase of the hydrostatic pressure. It is also found that the heat capacity of Au₂Al at low temperature strictly sticks to the Debye T³ law.     

Rotating magnetocaloric effect in HoAl2 single crystal

In this paper we theoretically discuss the rotating magnetocaloric effect in HoAl₂ single crystal. In order to do that, we use a model Hamiltonian of interacting magnetic moments including a term to account for the crystal electric field. Our theoretical calculations of the entropy changes are in a reasonable agreement with the available experimental data. Moreover, we predict the existence of an anomalous rotating magnetocaloric effect for some directions of the magnetic field rotation.     

The native point defects in C14 Mg2Ca Laves phase: A first-principles study

The native point defects in C14 Mg₂Ca Laves phase are studied from the first-principles density functional theory calculations within GGA approximation. The defect formation energies indicate that anti-site defects are energetically favored over vacancies. Under Mg-rich and even general Ca-rich condition, defect Mg_Ca of Mg anti-site on Ca sublattice is favorable owing to the lowest formation energy. The Ca_Mg2 defect of Ca anti-site on Mg2 sublattice is also likely dominant only under extreme Ca-rich environment. The present results could explain reasonably the asymmetric off-stoichiometry of Mg₂Ca. The effective point defect concentrations of Mg₂Ca as a function of composition and temperature at experimental range are also calculated from a canonical statistical model, and the derived results show a linear relationship between the logarithm of defect concentration and T⁻¹. Geometrical factor is further studied, and it is found that atomic size possesses an obvious influence on the structure of point defect in Mg₂Ca. The electronic feature is further studied to reveal underlying mechanism for formation of point defects.     

Synergistic effect of co-alloying elements on site preferences and elastic properties of Ni3Al: A first-principles study

The site preferences of co-alloying elements (Mo–Ta, Mo–Re, Mo–Cr) in Ni₃Al are studied using first-principles calculations, and the effects of these alloying elements on the elastic properties of Ni₃Al are evaluated by elastic property calculations. The results show that the Mo–Ta, Mo–Re and Mo–Cr atom pairs all prefer Al–Al sites and the spatial neighbor relation of substitution sites almost has no influence on the site preference results. Furthermore, the Young's modulus of Ni₃Al increases much higher by substituting Al–Al sites with co-alloying atoms, among which Mo–Re has the best strengthening effect. The enhanced chemical bondings between alloying atoms and their neighbor host atoms are considered to be the main strengthening mechanism of the alloying elements in Ni₃Al.