Characterization of the Fe-rich corner of Al-Fe-Si-Ti
The quaternary system Al-Fe-Si-Ti was studied in the iron-rich corner for sections at 50, 60 and 70 at.% Fe at 900 °C. Isothermal phase equilibria were investigated by a combination of optical microscopy, X-ray powder diffraction (XRD) followed by Rietveld refinement and Electron Probe Microanalysis (EPMA). Phase boundaries of the phases, in particular of the Laves phase (FeTi) and of the extended phase field of A2/B2/D0, were investigated. Selected samples containing the Laves phase and the B2 phase were characterized by microhardness measurements at different compositions throughout the quaternary homogeneity range of the phases.
Phase equilibria in the ternary In-Ni-Sn system at 700 °C
The phase equilibria of the ternary system In-Ni-Sn were investigated experimentally at 700 °C using X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron micro probe analysis (EMPA) and energy dispersive X-ray spectroscopy (EDX). A corresponding isothermal section was established based on these results. This particular temperature was chosen because it allowed obtaining reliable results within reasonable time. The existence of the ternary phase InNiSn was confirmed whereas the ternary compound InNiSn, reported earlier in literature, was found to be part of a large solid solution field based on binary InNi. The ternary solubility of the binary phases was established, and continuous solid solutions were found between the isostructural phases NiSn LT and InNi as well as between NiSn HT and InNi. In addition, this isothermal section could be well reproduced by CALPHAD modelling. The resulting calculated isotherm at 700 °C is presented, too, and compared with the experimental results.
The Cu-Sn phase diagram, Part I: New experimental results
Phase diagram investigation of the Cu-Sn system was carried out on twenty Cu-rich samples by thermal analysis (DTA), metallographic methods (EPMA/SEM-EDX) and crystallographic analysis (powder XRD, high temperature powder XRD). One main issue in this work was to investigate the high temperature phases beta (W-type) and gamma (BiF-type) and to check the phase relations between them. In the high temperature powder XRD experiments the presence of the two-phase-field between the beta- and the gamma-phase could not be confirmed. Detailed study of primary literature together with our experimental results leads to a new phase diagram version with a higher order transformation between these two high temperature phases. The present work is designated as part I of our joint publication. The new findings described here have been included into a completely new thermodynamic assessment of the Cu-Sn phase diagram which is presented in part II.
The Ni-rich part of the Al-Ge-Ni phase diagram
The Ni-rich part of the ternary system Al-Ge-Ni ( > 50 at.%) was investigated by means of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM). The two isothermal sections at 550 °C and 700 °C were determined. Within these two sections a new ternary phase, designated as τ4, AlGeNi (66, GaGeNi-type) was detected and investigated by single crystal X-ray diffraction. Another ternary low temperature phase, τ5, was found only in the isothermal section at 550 °C around the composition AlGeNi. This compound was found to crystallise in the CoSi type structure (12, ). The structure was identified by Rietveld refinement of powder data. The NiAs type (B8) phase based on binary GeNi revealed an extended solid solubility of Al and the two isotypic compounds AlNi and GeNi form a complete solid solution. Based on DTA results, six vertical sections at 55, 60, 70, 75 and 80 at.% Ni and at a constant Al:Ni ratio of 1:3 were constructed. Furthermore, the liquidus surface projection and the reaction scheme (Scheil diagram) were completed by combining our results with previous results from the Ni-poor part of the phase diagram. Six invariant ternary reactions were identified in the Ni-rich part of the system.
Phase equilibria and structural investigations in the Ni-poor part of the system Al-Ge-Ni
The ternary phase diagram Al-Ge-Ni was investigated between 0 and 50 at.% Ni by a combination of differential thermal analysis (DTA), powder- and single-crystal X-ray diffraction (XRD), metallography and electron probe microanalysis (EPMA). Ternary phase equilibria and accurate phase compositions of the equilibrium phases were determined within two partial isothermal sections at 400 and 700 °C, respectively. The two binary intermediate phases AlNi and AlNi were found to form extended solid solutions with Ge in the ternary. Three new ternary phases were found to exist in the Ni-poor part of the phase diagram which were designated as τ (oC24, CoGe-type), τ (at approximately AlGeNi) and τ (cF12, CaF-type). The ternary phases show only small homogeneity ranges. While τ was investigated by single crystal X-ray diffraction, τ and τ were identified from their powder diffraction pattern. Ternary phase reactions and melting behaviour were studied by means of DTA. A total number of eleven invariant reactions could be derived from these data, which are one ternary eutectic reaction, six transition reactions, three ternary peritectic reactions and one maximum. Based on the measured DTA values three vertical sections at 10, 20 and 35 at.% Ni were constructed. Additionally, all experimental results were combined to a ternary reaction scheme (Scheil diagram) and a liquidus surface projection.
Enthalpies of mixing of liquid systems for lead free soldering: Co-Sb-Sn
The partial and integral enthalpy of mixing of molten ternary Co-Sb-Sn alloys was determined performing high temperature drop calorimetry in a large compositional range at 1273 K. Measurements have been done along five sections, / ≈ 1:1, / ≈ 1:3, / ≈ 3:1, / ≈ 1:4, and / ≈ 1:5. Additionally, binary alloys of the constituent systems Co-Sb and Co-Sn were investigated at the same temperature. All the binary data were evaluated by means of a standard Redlich-Kister polynomial fit whereas ternary data were fitted on the basis of an extended Redlich-Kister-Muggianu model for substitutional solutions. An iso-enthalpy plot of the ternary system was constructed. In addition, the extrapolation Model of Toop was applied and compared to our data.
Phase equilibria and structural investigations in the system Al-Fe-Si
The Al-Fe-Si system was studied for an isothermal section at 800 °C in the Al-rich part and at 900 °C in the Fe-rich part, and for half a dozen vertical sections at 27, 35, 40, 50 and 60 at.% Fe and 5 at.% Al. Optical microscopy and powder X-ray diffraction (XRD) was used for initial sample characterization, and Electron Probe Microanalysis (EPMA) and Scanning Electron Microscopy (SEM) of the annealed samples was used to determine the exact phase compositions. Thermal reactions were studied by Differential Thermal Analysis (DTA). Our experimental results are generally in good agreement with the most recent phase diagram versions of the system Al-Fe-Si. A new ternary high-temperature phase (96, NiTi-type) with the composition AlFeSi was discovered and was structurally characterized by means of single-crystal and powder XRD. The variation of the lattice parameters of the triclinic phase with the composition Al FeSi (-0.3 < < 1.3) was studied in detail. For the binary phase FeSi only small solubility of Al was found in the low-temperature modification LT-FeSi ( ) but significant solubility in the high-temperature modification HT-FeSi ( ) (8.5 at.% Al). It was found that the high-temperature modification of FeSi is stabilized down to much lower temperature in the ternary, confirming earlier literature suggestions on this issue. DTA results in four selected vertical sections were compared with calculated sections based on a recent CALPHAD assessment. The deviations of liquidus values are significant suggesting the need for improvement of the thermodynamic models.
Re-investigation of phase equilibria in the system Al-Cu and structural analysis of the high-temperature phase η-AlCu
The phase equilibria and reaction temperatures in the system Al-Cu were re-investigated by a combination of optical microscopy, powder X-ray diffraction (XRD) at ambient and elevated temperature, differential thermal analysis (DTA) and scanning electron microscopy (SEM). A full description of the phase diagram is given. The phase equilibria and invariant reactions in the Cu-poor part of the phase diagram could be confirmed. The Cu-rich part shows some differences in phase equilibria and invariant reactions compared to the known phase diagram. A two phase field was found between the high temperature phase η and the low temperature phase η thus indicating a first order transition. In the ζ/ζ region of the phase diagram recent findings on the thermal stability could be widely confirmed. Contrary to previous results, the two phase field between δ and γ is very narrow. The results of the current work indicate the absence of the high temperature β phase as well as the absence of a two phase field between γ and γ suggesting a higher order transition between γ and γ. The structure of γ (-43, CuZn-type) was confirmed by means of high-temperature XRD. Powder XRD was also used to determine the structure of the high temperature phase η-AlCu. The phase is orthorhombic (space group ) and the lattice parameters are = 4.1450(1) Å, = 12.3004(4) Å and = 8.720(1) Å; atomic coordinates are given.
Experimental investigation of the Cu-Si phase diagram at (Cu)>0.72
Cu-Si phase equilibria have been investigated at compositions greater than 72 at.% Cu by X-ray diffraction, optical and electronic microscopy, electron probe microanalysis and differential thermal analysis. The general aspects of the phase equilibria already reported in literature have been substantially confirmed, but selected composition ranges and the nature of a few invariant equilibria have been modified. In particular stability ranges of the , and phases have been slightly modified as well as temperature and nature of the invariant equilibria related to the ⇄ transformation. Stability of the ɛ-(CuSi) phase has been especially investigated concluding that it is thermodynamically stable but kinetically inhibited by nucleation difficulties which become especially effective when samples are synthesized in very high purity conditions. Crystal structure and composition ranges of the high temperature and phases, despite difficulties by the non-quenchability of these phases, have been investigated by different methods including high temperature XRD.
The high-temperature phase equilibria of the Ni-Sn-Zn system: Isothermal sections
In this work three complete isothermal sections of the Ni-Sn-Zn system at 700, 800 and 900 °C are presented. They were constructed based on experimental investigation of more than 60 alloy samples. Powder XRD, single crystal XRD, EPMA, and DTA measurements on selected samples were carried out. Two new ternary compounds, designated as τ2 (NiSnZn) and τ3 (NiSnZn), were identified and their homogeneity ranges and crystal structures could be described. Whereas τ3 is only present at 700 °C, the τ2-phase was found at both 700 and 800 °C. No truly ternary compound could be found in the isothermal section at 900 °C. A seemingly ternary compound at 20 at% Sn in the Ni-rich part of Ni-Sn-Zn was found at 800 and 900 °C. Our XRD results, however, indicate that this phase is a ternary solid solution of NiSn-HT from constituent binary Ni-Sn. It is stabilized to lower temperatures by additions of Zn. These new experimental results will provide valuable information to the thermodynamic description of alloy systems relevant for high-temperature lead-free soldering.
Study of reorientation processes in L1-ordered FePt thin films
We report on the development of structural and magnetic order in epitaxially grown L1 FePt thin films. Upon annealing, the easy axis of magnetization changes from the out-of-plain into the in-plain direction. We found that the overall fraction of reoriented domains first increases but after certain time decreases before achieving a saturated state. The results are based on conversion electron Mössbauer spectroscopy studies and confirm Monte Carlo simulations in nano-layered FePt. We present a modified version of the Johnson-Mehl-Avrami (JMA) model adequately describing the experimental findings. Two dynamical processes, the first being a 2D-growth, dominate the initial state of sample annealing and the second being a 3D-growth, dominate the late stage close to saturation. From an Arrhenius plots of JMA coefficients for both processes we extracted the activation energies of the underlying dynamics which are 1.5(1) eV for disordering and 0.8(2) eV for ordering.
Thermodynamic analysis of the topologically close packed σ phase in the Co-Cr system
Density functional theory (DFT) calculations show that it is essential to consider the magnetic contribution to the total energy for the end-members of the σ phase. A more straightforward method to use the DFT results in a CALPHAD (Calculation of phase diagrams) description has been applied in the present work. It was found that only the results from DFT calculations considering spin-polarization are necessary to obtain a reliable description of the σ phase. The benefits of this method are: the DFT calculation work can be reduced and the CALPHAD description of the magnetic contribution is more reliable. A revised thermodynamic description of the Co-Cr system is presented which gives improved agreement with experimental phase boundary data for the σ phase.
