Thermophysical properties of Cu–In–Sn liquid Pb-free alloys: viscosity and surface tension

The viscosity of a few Cu–In–Sn liquid alloys has been investigated by a number of geometric (Muggianu, Kohler, Toop) and physical thermodynamic models (Kozlov–Romanov–Petrov, Budai–Benko–Kaptay, Schick et al.) and GSM for the cross section (z/y = 1/3) in Pb-free liquid alloy Cu_x–In_y–Sn_z at 1073 K. Moreover, the surface tensions of the same liquid alloys have been investigated by a number of geometric models and the Butler model for the cross section Cu_x–In_y–Sn_z (z/(y + z) = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) at the same temperature. The best agreement of the surface tensions was obtained in the Kohler model for x_Cu = 10 at % and the Butler model for x_Cu = 20 at % and x_Cu = 30 at.%, respectively. The best agreement among chosen geometric and physical models and experiment for these selected sections Cu₈₀In₁₅Sn₅, Cu₇₅In₁₅Sn₁₀, Cu₅₅In₇Sn₃₈, Cu₃₃In₅₀Sn₁₇ and Cu₂₆In₅₅Sn₁₉ at 1073 K was obtained for the Budai–Benkö–Kaptay model.     

Geometric modelling of viscosity of copper-containing liquid alloys

In this work, viscosities of ternary Au–Ag–Cu and Al–Cu–Si liquid alloys have been calculated as a function of gold, aluminium and copper compositions for the sections Au–Ag–Cu (x_Ag/x_Cu = 0.543 at 1373 K), Al_x(Cu₅₀–Si₅₀)_(1–x) and Cu_x(Al₅₀–Si₅₀)_(1–x) at 1375 K using Chou’s general solution model, Muggianu, Kohler, Toop, Hillert, Budai et al., Kozlov et al., Schick et al. and Kaptay et al. models. The present study finds that a comparison of the predicted values of viscosities associated with the geometric and physical models indicate good mutual agreement. The Muggianu model indicates the best agreement with the results obtained for Au–Ag–Cu and Al_x–Cu₅₀–Si₅₀ alloy systems and the Kaptay et al. model, which is a physical model, indicates the best agreement with the results obtained for Al₅₀–Cu_x–Si₅₀.     

Tendency of metallic crystals to amorphization in the process of severe (Megaplastic) deformation

The main features of the transition of crystalline Ni₅₀Ti₃₀Hf₂₀, Ti₅₀Ni₂₅Cu₂₅, Zr₅₀Ni₁₈Ti₁₇Cu₁₅, and Fe₇₈B_8.5Si₉P_4.5 alloys with various tendencies to amorphization into an amorphous state upon melt quenching and in the course of severe deformation in Bridgman anvils have been considered. The crystalline state of these alloys has been produced using various methods of annealing. In the iron-based alloy, single-phase and two-phase crystalline states have been studied. The nickel- and titanium-based alloys after annealing were in a single-phase crystalline state; the zirconium-based alloy, in a two-phase state. It is shown that at the same degree of deformation the rates of amorphization of crystalline alloys differ substantially; namely, the single-phase crystalline titanium- and iron-based alloys amorphize easily, whereas the Zr-based alloy amorphizes only poorly, just like the two-phase iron-based alloy. It can be assumed that the tendency to deformation-induced amorphization of crystalline alloys and the corresponding crystalline phases is mainly determined by three factors: mechanical, thermodynamic, and concentration-related.     

Research on Zr50Al15−xNi10Cu25Yx amorphous alloys prepared by mechanical alloying with commercial pure element powders

Amorphous Zr₅₀Al_15−xNi₁₀Cu₂₅Y_x alloy powders were fabricated by mechanical alloying at low vacuum with commercial pure element powders. The effects on glass forming ability of Al partial substituted by Y in Zr₅₀Al₁₅Ni₁₀Cu₂₅ and thermal stability of Si₃N₄ powders addition were investigated. The as-milled powders were characterized by X-ray diffraction, scanning electron microscopy and differential scanning calorimeter. The results show that partial substitution of Al can improve the glass forming ability of Zr₅₀Al₁₅Ni₁₀Cu₂₅ alloy. Minor Si₃N₄ additions raise the crystallization activation energy of the amorphous phase and thus improve its thermal stability.     

Magnetic interference effect in amorphous D-band metals with high electrical resistivity

Systematic occurence of low temperature resistivity anomalies (upturn) in amorphous alloys Zr₅₀Cu₅₀, Zr₇₅Ni₂₅, and Y₇₅A?₂₅ containing up to 4 at .% Gd is observed. Detailed analysis of ‘background’ impurity (other than Gd) effects on the electrical resistivity of the alloy host Zr₅₀Cu₅₀ provides unambiguous evidence that the anomalies are due solely to the Gd ions. The present results are interpreted in terms of conduction electrons with short mean free path scattering from nearest neighboring pairs of Gd spins. Predictions derived from the diffraction type model of magnetic interference, however, fail to describe all the results on metals with high electrical resistivity. Data on Zr₅₀Cu₅₀ containing Fe and Mn are also discussed.     

Susceptibility of crystalline alloys to deformational amorphization during torsion under quasi-hydrostatic pressure

Features of the transition of Ni₅₀Ti₃₀Hf₂₀, Ti₅₀Ni₂₅, Zr₅₀Ni₁₈Ti₁₇Cu₁₅, and Fe₇₈B_8.5Si₉P_4.5 crystalline alloys with different susceptibilities to amorphization upon annealing and in the amorphous state during intense deformation in a Bridgman chamber are considered. The single- and two-phase crystalline states of the chosen alloys are obtained in different annealing modes. It is shown that the amorphizing rate of crystalline alloys differ substantially at the same degree of deformation; i.e., single-phase crystalline alloys based on titanium nickelide and iron amorphize well, while zirconium-based alloy amorphizes weakly in a manner similar to two-phase iron alloy. We believe that the LDA of crystalline alloys and their corresponding crystalline phases is determined by mechanical, thermodynamic, and concentration factors.     

Determination of the magnetocaloric effect associated with martensitic transition in Ni46Cu4Mn38Sn12 and Ni50CoMn34In15 Heusler alloys

This paper presents a study of the inverse magnetocaloric effect (MCE) corresponding to martensitic transition using various experimental approaches for Ni46Cu4Mn38Sn12 and Ni50CoMn34In15 Heusler alloy. Through heat capacity measurements,it is found that the "giant inverse MCE" upon martensitic transition evaluated by the Maxwell relation in these alloys are unphysical results. This is due to the coexistence of both martensitic and austenitic phases,as well as thermal hysteresis during martensitic transition. However,careful study indicates that the spurious results during martensitic transition can be removed using a Clausius-Clapeyron equation based on magnetization measurements.     

Effect of Gd and Fe doping on magnetic properties of Al87Y5Ni8 amorphous alloy

In this paper we present and discuss magnetic properties of the Al₈₇Y₅Ni₈, Al₈₇Y₄Gd₁Ni₈, Al₈₇Gd₅Ni₈, Al₈₇Y₄Gd₁Ni₄Fe₄ and Al₈₇Gd₅Ni₄Fe₄ amorphous alloys. The examinations have been concentrated on a possible magnetic ordering at low temperatures and its modification by amorphous surroundings as well as different magnetic moment of alloying additions. It was shown that magnetic properties of the Al₈₇Y₅Ni₈ amorphous base alloy correspond to a superparamagnetic body with Ni magnetic clusters. Magnetic moment of Ni atom in amorphous aluminum matrix is found to be 0.3 μ_B that corresponds to less than 50 Ni atoms per one cluster. Gd doping of the base alloy leads to a decrease of the resultant magnetic moment of Ni clusters that can be explained by some antiferromagnetic coupling Ni-Gd and Ni-Ni within magnetic clusters.     

Predicting macroscopic thermal expansion of metastable liquid metals with only one thousand atoms

Results of thermal expansion prediction from atomic scale for metastable liquid metals are reported herein. Three pure liquid metals Ni, Fe, and Cu together with ternary Ni₆₀Fe₂₀Cu₂₀ alloy are used as models. The pair distribution functions were employed to monitor the atomic structure. This indicates that the simulated systems are ordered in atomic short range and disordered in long range. The thermal expansion coefficient was computed as functions of temperature and atom cutoff radius, which tends to maintain a constant when the cutoff radius increases to approximately 15 Å. In such a case, slightly more than 1000 atoms are required for liquid Ni, Cu, Fe and Ni₆₀Fe₂₀Cu₂₀ alloy, that is, the macroscopic thermal expansion can be predicted from the volume change of such a tiny cell. Furthermore, the expansion behaviors of the three types of atoms in liquid Ni₆₀Fe₂₀Cu₂₀ alloy are revealed by the calculated partial expansion coefficient. This provides a fundamental method to predict the macroscopic thermal expansion from the atomic scale for liquid alloys, especially in the undercooled regime.     

A comparative study of the structure and crystallization of bulk metallic amorphous rod Pr60Ni30Al10 and melt-spun metallic amorphous ribbon Al87Ni10Pr3

Pr-based bulk metallic amorphous （BMA） rods （Pr60Ni30Al10） and Al-based amorphous ribbons （Al87Ni10Pr3） have been prepared by using copper mould casting and single roller melt-spun techniques, respectively. Thermal parameters deduced from differential scanning calorimeter （DSC） indicate that the glass-forming ability （GFA） of Pr60Ni30Al10 BMA rod is far higher than that of Al87Ni10Pr3 ribbon. A comparative study about the differences in structure between the two kinds of glass-forming alloys, superheated viscosity and crystallization are also made. Compared with the amorphous alloy Al87Ni10Pr3, the BMA alloy Pr60Ni30Al10 shows high thermal stability and large viscosity, small diffusivity at the same superheated temperatures. The results of x-Ray diffraction （XRD） and transmission electron microscope （TEM） show the pronounced difference in structure between the two amorphous alloys. Together with crystallization results, the main structure compositions of the amorphous samples are confirmed. It seems that the higher the GFA, the more topological type clusters in the Pr-Ni-Al amorphous alloys, the GFAs of the present glass-forming alloys are closely related to their structures.     

Atomic configuration of microtwins in alloys having Ll2 superstructure

In the approximation of paired interatomic potentials of the Morse type, modeling is done on the atomic configuration and energy of formation of superstructure stacking faults and superstructure twinning stacking faults in the ordered alloys Cu₃Au and Ni₃Fe, and also in the intermetallide Ni₃Al. Features are observed in the local deformation of the crystal lattice defects near equilibrium (in terms of internal energy), and the principle difference in the state of the atomic surroundings of the examined plane defects is shown. In alloys of Cu₃Au and Ni₃Fe, calculations are done for different values of the long-range order parameter. A difference is detected in the variation of the energy of formation of superstructure twinning stacking faults in alloys of Cu₃Au and Ni₃Fe with the long-range order parameter. This difference correlates with experimental observation of the properties when varying the temperature in the alloys.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 31–36, November, 1987.     

The fine structure of FCC nanocrystals in Al-and Ni-based alloys

The structural perfection of nanocrystals in alloys of different chemical composition is studied by x-ray diffraction and high-resolution electron microscopy. In all the alloys studied, crystallization of the amorphous phase produces a nanocrystalline structure. The nanocrystal size depends on the chemical composition of the alloy and varies in aluminum-based alloys from 5 nm in Al₈₉Ni₅Y₆ to 12 nm in Al₈₂Ni₁₁Ce₃Si₄. Nanocrystals in nickel-based alloys vary in size from 15 to 25 nm. Al nanocrystals are predominantly defect-free, with microtwins observed only in some nanocrystals. The halfwidth of the diffraction lines is proportional to sec θ, which implies the small grain size provides the major contribution to the broadening. Nanocrystals in nickel alloys contain numerous twins, stacking faults, and dislocations.     

Size effect on the structure of Al-and Ni-based nanocrystals

The structure of nanocrystals formed upon crystallization of amorphous alloys of the Ni-Mo-B and Al-Ni-RE systems (RE = Y, Yb, Ce) was studied using x-ray diffraction and high-resolution transmission electron microscopy. It is shown that the lattice parameters and the existence of structural defects depend on the alloy composition and heat treatment conditions. At the beginning of crystallization, all nanocrystals are defectless. After the first stage of crystallization is completed, the aluminum nanocrystals remain perfect, whereas the nanocrystals of molybdenum solid solution contain numerous defects. It is revealed that the nanocrystals of the same size in different systems are either defectless (Al₈₂Ni₁₁Ce₃Si₄, Al₈₈Ni₁₀Y₂, etc.) or contain numerous defects (Ni₇₀Mo₃₀)₉₀B₁₀.     

Au/In bilayers studied with 111In deposited at the interface

Au/In bilayer samples of different stoichiometries were studied using the time-differential perturbed angular correlation technique. The ¹¹¹In probe atoms were deposited at the gold/indium interface to follow the formation of the intermetallic compounds at an early stage. Au-In phases of different composition (AuIn₂, AuIn, Au₇In₃, Au₃In) were created at the interfaces upon annealing. In addition a metastable Au₇In₃(m) phase, observed only after quenching in the bulk Au_0.7In_0.3 alloy, was found. This revised version was published online in August 2006 with corrections to the Cover Date.     

Severe plastic deformation of amorphous alloys: II. Magnetic properties

The influence of severe plastic deformation in a Bridgman cell on the magnetic properties of amorphous alloys of metal-metalloid type, Ni₄₄Fe₂₉Co₁₅Si₂B₁₀, Fe₇₄Si₁₃B₉Nb₃Cu₁, Fe_57.5Ni₂₅B_17.5, Fe_49.5Ni₃₃B_17.5, and Fe₇₀Cr₁₅B₁₅, obtained by melt spinning, has been investigated. It is found that the saturation magnetization significantly changes (increases or decreases), depending on the number of ferromagnetic and antiferromagnetic components in the alloy. It is suggested that very high shear stress causes internal phase decomposition in the amorphous matrix into nanoscale regions, enriched or depleted with ferromagnetic components.     

Mössbauer spectroscopy study of the disordering process of Fe-rich FeAlSi alloys

In this work we study systematically the influence of different Al/Si ratios on the magnetic and structural properties of mechanically disordered powder Fe₇₅Al_25?x Si _x , Fe₇₀Al_30?x Si _x and Fe₆₀Al_40?x Si _x alloys by means of Mössbauer spectroscopy and X-ray diffraction measurements. In order to obtain different stages of disorder the alloys were deformed by ball milling annealed (ordered) alloys during different number of hours. X-ray and Mössbauer data show that mechanical deformation induces the disordered A2 structure in these alloys. The results indicate that addition of Si to binary Fe–Al alloys makes the disordering more difficult. The study of the hyperfine fields indicates that depending on the Fe content the magnetic behaviour of these ternary alloys varies. For Fe₇₅Al_25?x Si _x series, the alloys have different magnetic behaviours with deformation depending on the Si content. The magnetization of the alloys with high Si content decreases with deformation, as it happens to binary Fe₇₅Si₂₅ and the magnetization of the alloys with low Si content increases with deformation, as it happens to binary Fe₇₅Al₂₅. For Fe₇₀Al_30?x Si _x series the mean hyperfine fields show that there are two different stages with the disordering, in a first stage the mean hyperfine fields decrease and in the second stage they increase. Finally, for Fe₆₀Al_40?x Si _x alloys there is a magnetic transition, from a paramagnetic ordered state to a magneticdisordered state.     

Effect of ion sputtering on the surface composition of indium-lead and indium-tin alloys

The effect of argon ion sputtering on the surface composition of a series of InPb and InSn single phase alloys (In_0.998Pb_0.002, In_0.5Pb_0.5, In_0.1Pb_0.9, In_0.9Sn_0.1, and In_0.02Sn_0.98) has been examined by Auger electron spectroscopy. The results are consistent with the hypothesis that the alloy component with the higher binding energy, i.e., the higher heat of atomization, becomes enriched in the near surface region.     

Grain oriented NiMnSn and NiMnIn Heusler alloys ribbons produced by melt spinning: Martensitic transformation and magnetic properties

We outline the microstructural, martensitic transformation and magnetic properties of Heusler alloys with starting compositions Ni₅₀Mn₃₇Sn₁₃, Ni₅₀Mn₃₆In₁₄, and Mn₅₀Ni₄₀In₁₀, produced by melt spinning. The ribbons were obtained in argon environment at a high wheel linear speed of 48 m s⁻¹ (typical dimensions: 1.2-2.0 mm in width, 4-12 mm in length, and 7-12 μm in thickness). EDS microanalysis showed that the resulting average elemental chemical composition is slightly shifted with respect to the starting one. Ribbons are fully crystalline and tend to show a highly ordered columnar-like microstructure with grains running through the entire ribbon thickness; the larger dimension of the grains is perpendicular to the ribbon plane. As-spun alloys were single-phase with ferromagnetic bcc L2₁ austenite as high-temperature parent phase. At low temperatures austenite transforms into a structurally modulated martensite with a lattice symmetry that depends on the system (7 M orthorhombic for Ni₅₀Mn₃₇Sn₁₃, 10 M monoclinic for Ni₅₀Mn₃₆In₁₄, and 14 M monoclinic for Mn₅₀Ni₄₀In₁₀). Magnetization isotherms measured in the temperature interval where martensite thermally transforms into austenite confirmed the occurrence of field-induced reverse martensitic transition in the alloys studied.     

Crystal-field induced anomalies in the thermoelectric power and electrical resistivity of amorphous cerium alloys

The amorphous alloys Ce₇₂Cu₂₈, Ce₈₀Au₂₀ and Ce₈₉Al₁₁ exhibit a pronounced maximum in the thermoelectric power near 50 K, together with a step-like increase of the electrical resistivity. This is interpreted in terms of a model invoking Kondo scattering from the cerium 4f states split by the local crystal fields of the amorphous matrix. The data for the alloys with Cu and Au indicate a narrow distribution of the overall crystalfield splittings. This hints at a rather uniform structural short-range order.     

Ion-beam induced mixing of Cu/Au bilayer thin film (kinematics and formation of solid solutions)

Ion-beam induced atomic mixing of Cu/Au bilayer thin film is studied using combined electrical resistivity measurements and Rutherford Backscattering Spectrometry (RBS). 400 keV Kr⁺ ion irradiation with fluences ranging from 3.3×10¹⁵ to 7.6×10¹⁶ ions/cm² at room temperature have been used. Ion beam mixing lead to a uniformly mixed metal alloy. The formation of Cu/Au solid solutions depends on the initial composition and on the fluence of irradiating ions. For an initial composition of Cu₄₂Au₅₈, a Cu-rich solid solution of composition Cu₇₂Au₂₈ is formed after irradiation with 7.6×10¹⁶ ions/cm². The kinematics of the intermixing process is also studied by in situ electrical resistivity measurements which confirmed the formation of the Cu/Au solid solutions.