Thermodynamic characterization of Al–Cr,Al–Zr,and Al–Cr–Zr alloy systems

Abstract

The equilibrium phase diagrams of Al–Cr, Al–Zr, and Al–Cr-Zr, with particular reference to aluminium-rich alloys, have been critically reviewed. On the basis of these, and consistent with measured thermodynamic values, the binary systems have been thermodynamically characterized. Using these characterizations, phase equilibria have been extrapolated in the ternary, with the intention of augmenting the sparse experimental information concerning the equilibrium liquidus (0–10 at.%Cr, Zr) and solid solution range of aluminium in Al–Cr–Zr. Using the same parameters that define the equilibrium phase relationships, metastable phase relationships can also be extrapolated into the ternary.

MST/418     

Experimental investigation and thermodynamic assessment of the Mg–Zn–Gd system focused on Mg-rich corner

The phase equilibria in the Mg-rich corner of Mg–Zn–Gd ternary system at 673 K were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), and electron probe microanalysis (EPMA). Three ternary phases, X-(Mg₁₂ZnGd), W-(Mg₃Zn₃Gd₂) and I-(Mg₃Zn₆Gd₁), have been identified, which are in equilibrium with Mg solid solution. A thermodynamic modeling and optimization of Zn–Gd and Mg–Zn–Gd systems has been carried out for the first time using the CALPHAD method. The sublattice model was used to describe the thermodynamic functions of both solution phases and intermetallic phases presented in these systems. In particular, order/disorder transition between BCC_B2 and BCC_A2 has been taken into account, and their Gibbs energies were expressed with identical function. The thermodynamic database was applied to case studies of experimentally observed microstructures and demonstrated that it is a valuable basis for alloy design.     

Resulting morphologies on quenching of titanium aluminide alloys

Abstract

The effect of alloying elements (aluminium, silicon, niobium, and zirconium) on the mechanism and morphology of the allotropic transformation Ti-β(bcc) → Ti-α(hcp), occurring during the quenching of binary, ternary, and quaternary titanium aluminide alloys, has been studied. The alloys investigated were (at.-%) Ti–16Al, Ti–16Al–1Si, Ti–16Al–3·5Si, Ti–14Al–1Si–1Nb, Ti–14Al–1Si–1Zr, Ti–22Al, Ti–22Al–1Si, Ti–22Al–3·5Si, Ti–20Al–1Si–1Nb, and Ti–20Al–1Si–1Zr. The allotropic transformation in these alloys presented a very narrow temperature range for the formation of all possible α morphologies resulting from quenching. The different morphologies of α phase observed have been correlated with the competing mechanisms of β decomposition. The morphological observations indicated that small variations in thermodynamic and kinetic conditions in the β phase might account for changes in the mechanisms of formation and growth of the α phase. Additionally, the effect of the alloying elements on the ordering reaction α → α₂ occurring during quenching has been investigated. Silicon addition promoted the formation of columnar α₂ domains during quenching.     

'Spalling' of SAC Pb free solders when used with nickel substrates

Abstract

The term "spalling" refers to the formation in a solder joint of a second layer of intermetallic compound, in addition to and separate from the usual single layer that normally forms on the substrate. It has been observed in Pb-free solders of the SAC type when used in conjunction with a nickel finish. Explanations offered to account for this phenomenon have been based on thermodynamic phase equilibria observed in isothermal sections of the Sn corner of the Cu–Ni–Sn system at temperatures 20°C or more above the solidification temperature of the solder, and without regard to reactions that occur at low temperatures, during freezing. Recent measurement of the liquidus projection of the Sn corner of the Cu–Ni–Sn system as shown the occurrence of a ternary quasiperitectic reaction in the composition range in which "spalling" is observed. Evaluation of the effect of this quasiperitectic reaction shows that its operation during freezing of the solder can account for the "spalling" phenomenon.     

Experimental study and thermodynamic modeling of the Al–Co–Cr–Ni system

Abstract

A thermodynamic database for the Al–Co–Cr–Ni system is built via the Calphad method by extrapolating re-assessed ternary subsystems. A minimum number of quaternary parameters are included, which are optimized using experimental phase equilibrium data obtained by electron probe micro-analysis and x-ray diffraction analysis of NiCoCrAlY alloys spanning a wide compositional range, after annealing at 900 °C, 1100 °C and 1200 °C, and water quenching. These temperatures are relevant to oxidation and corrosion resistant MCrAlY coatings, where M corresponds to some combination of nickel and cobalt. Comparisons of calculated and measured phase compositions show excellent agreement for the β–γ equilibrium, and good agreement for three-phase β–γ–σ and β–γ–α equilibria. An extensive comparison with existing Ni-base databases (TCNI6, TTNI8, NIST) is presented in terms of phase compositions.     

Simulation of microsegregation and microstructural evolution in directionally solidified superalloys

Abstract

A two-dimensional model for solidification and secondary phase precipitation in directionally solidified superalloys is presented, which makes use of a shape function approximation for the isothermal cross-section of the primary dendrites. The phase boundary is represented by a diffuse interface on a finite difference grid, as in phasefield methods. Thus, two-dimensional multicomponent diffusion can be calculated for all phases. Via a Fortran interface, the model is coupled to thermodynamic databases assessed using the ‘calculation of phase diagrams’ (Calphad) approach. In this way, for each time step actual data are available for partitioning, dendritic growth, and nucleation of secondary phases. The model is applied to Ni–Al–Cr as a ternary model system and to the commercial superalloy IN706.     

Tie line compositions of ternary Cu–Ag–Au alloys within miscibility gap

Abstract

Tie line coordinates of ternary Cu–Ag–Au alloys in the solid immiscible region of the equilibrium phase diagram were determined experimentally by electron probe microanalysis. The two solid phases were analysed in samples which had been thermally treated from the as–cast condition to coarsen the phases. Tie line coordinates were also calculated theoretically using a thermodynamic model which is an extension of the regular solution model. The theoretical calculations agree well with the experimental analysis of the copper–rich phase as well as with a corrected analysis of the silver–rich phase. The necessity for the correction was attributed to the thermal coarsening treatment of the samples.

MST/191     

Mechanical and chemical properties of Ni3Si and Ni3(Si,Ti) alloys multiphased by chromium addition

Abstract

The alloying behaviour and microstructure of Ni–Si–Cr ternary and Ni–Si–Ti–Cr quaternary alloys were first characterised by optical microscopy, X-ray diffraction, and scanning electron microscopy with electron probe analysis. The microstructures of the Ni–Si–Cr ternary alloys consisted of large dispersed Ni₅Si₂ phase and finely precipitated Ni₃Si phase in nickel solid solution, while the Ni–Si–Ti–Cr quaternary alloys consisted of finely precipitated Ni₃(Si,Ti) phase and nickel solid solution. Then, the high temperature mechanical properties, bend strength, and oxidation and corrosion properties of the alloys were investigated. The Ni–Si–Cr ternary alloys showed significant strengthening over a wide range of temperatures, and also large compressive plastic deformation at high temperatures. The strength and fracture toughness at ambient temperatures were correlated with the volume fraction of Ni₅Si₂ phase. The Ni–Si–Ti–Cr quaternary alloys did not show increased yield strength, but exhibited improved tensile ductility and plasticity over a wide range of temperatures. Both Ni–Si–Cr ternary and Ni–Si–Ti–Cr quaternary alloys showed substantially improved oxidation resistance in air at 1173 K, compared with Ni₃Si and Ni₃(Si,Ti) alloys. Also, the Ni–Si–Cr ternary and Ni–Si–Ti–Cr quaternary alloys showed corrosion resistance comparable to that of the Ni₃Si and Ni₃(Si,Ti) alloys.     

Solid state phase transformations in Ti–Al–C and Ti–Al–Nb–C alloys

Abstract

Results are reported of an investigation of solid state transformations in a series of α₂ based alloys having an aluminium content of 26 at.-% with carbon up to 3 at.-%; two α₂ basedquaternary Ti–Al–Nb–C alloys with 5 and 12 at.-%Nb and 3 at.-%C were also studied. Ordering occurs in the ternary Ti–Al–C alloys and also in the 23Al–5Nb–3C alloy on quenchingfrom 1250°C. Additional carbide precipitation was not observed in the ternary Ti–Al–C alloys on reheating to 750°C. Additions of niobium resulted in the presence of the β phase at 1050°C in the 5%Nb alloy and at 1050 and 750°C in the 12%Nb alloy. In the quaternary Ti–Al–Nb–C alloys, (Ti, Nb)₃AlC was found to be the primary phase and was present in the microstructure over the temperature range studied. In the 21Al–12Nb–3C alloy, the ordered β phase transformed to α″₂ martensite on quenching from 1250;amp;#x00B0;C.

MST/1306     

The primary ice phase field in the H2O-NaCl-dimethyl sulphoxide ternary system

The determination and application of H₂O-NaCl-cryoprotective agent phase diagram information appears to be a fruitful area for co-operative research between materials scientists and biologists. Dimethyl sulphoxide (DMSO) is a widely used cryoprotective agent, and in this present work the primary ice phase field in the H₂O-NaCl-DMSO system has been determined including the extension into this system of the lines of two-fold saturation from the ice-NaCl · 2H₂O and the ice-DMSO · 3H₂O binary eutectics. Liquidus surface data are presented for isoplethal sections taken through the ternary system along composition lines defined by weight ratios of DMSO to NaCl of 1/5, 1/2 and 9. Liquidus surface data obtained from an additional thirteen isoplethal sections are used to construct the complete isothermal projections of the primary ice phase field along 10° C contours. The distribution and occurrence of glassy phases in this ternary system are also discussed.     

Experimental study of Bi–Cd–In phase diagram using conventional methods plus quenching and ‘solidification path’ techniques

Abstract

The liquidus projection of the Bi–Cd–In ternary alloy system has been redetermined, using the conventional methods of thermal analysis and differential scanning calorimetry, as well as quenching experiments and a ‘solidification path’ technique. In the latter method, specimens were solidified unidirectionally at a very low speed in order to maintain a coherent solid/liquid interface while approximating freezing with complete mixing in the liquid. This produced macroscopic segregation that clearly revealed the phases formed on a scale suitable for straightforward chemical analysis in a scanning electron microscope. Two quasibinary sections were found, one of which (BiIn₂–Cd) divides the system into two independent regions. A newly discovered ternary phase, designated Z, as well as several previously unreported ternary four phase reactions of the quasiperitectic type, were observed. The Bi–Z join was found to be a quasibinary peritectic section. A number of solid state reactions of the eutectoid type were also noted.     

Calculation of thermodynamics properties in the Al–Co–Me (Me=Ti,Mo) systems,in the liquid phase

Abstract

The results of calculation using thermodynamic predicting for ternary systems Al–Co–Ti and Al–Co–Mo are presented in this paper. Characteristic thermodynamic properties, including integral and partial molar quantities at different temperatures, have been calculated using Redlich–Kister–Mugginanu method and general solution model.     

Equilibria involving P- and (σ-phases in Ni–Cr–Al–Mo system

Abstract

An investigation is reported of phase equilibria in alloys of the Ni–Cr–AI–Mo system containing 60 and 50 at. –%Ni annealed at 1523 K. The experimental methods used mainly were electron microscopy, electron probe microanalysis, and X–ray diffraction. Four quaternary alloys were used, with compositions (at.–%) lying on a line between Ni₆₀Al₄₀ and Ni₆₀Cr₂₀Mo₂₀,and one alloy containing 50Ni–28Cr–10AI-12Mo.The composition range was chosen to include the P–and σ –phases based on the Ni–Cr–Mo system. The phases involved in equilibria at 1523 K in the 60 at. –%Ni alloy series were γ (Ni–base solid solution), β (based on NiAI), Mo–base solid solution, and P; the 50 at. –%Ni alloy contained γ, β and σ. Partial isothermal sections of the quaternary system at 60 and 50 at. –%Ni have been determined. Eutectics containing either γ + P or γ + β + P were present

in the as–solidified 60 at. –%Ni alloys, while a γ + β + σ eutectic was present in the 50 at–%Ni alloy; some compositional data for eutectic phases were obtained by analytical transmission electron microscopy. High hardness values (from ~ 500 to 670 HV) were obtained in the as–solidified alloys.

MST/265     

Experimental investigation and thermodynamic description of the Mg–Y–Zr system

The Mg–Y–Zr system was studied via experimental investigation and thermodynamic modeling. Four diffusion couples and four key alloys of the Mg–Y–Zr system at 500 °C were prepared. The phase relations of the Mg–Y–Zr system were investigated by means of X-ray diffraction, scanning electron microscopy, and electron probe microanalysis. No ternary compound was found at 500 °C. The solubility of (αZr) in the Mg–Y intermetallics, i.e., Mg₂₄Y₅, Mg₂Y and MgY, was determined to be negligible. The differential scanning calorimetry measurement was performed on the Mg–Y–Zr alloys to obtain the phase transition temperature. The present thermodynamic calculations of the Mg–Y–Zr system matched well with the experimental data. The presently established Mg–Y–Zr phase diagram can offer a better understanding of the recent processing technique of creep-resistant magnesium alloys.     

Thermodynamic evaluation of Nb–C system

Abstract

The thermodynamic properties and the phase diagram of the Nb–C system have been assessed using thermodynamic models for the Gibbs energy of all the stable phases. An optimum set of thermodynamic parameters reproducing consistently most of the available experimental information has been obtained.

MST/1153     

Fe–AI–Zn ternary phase diagram at 450°C

Abstract

Several Fe–Al and Fe–Al–Zn alloys were vacuum melted, annealed at 450°C under atmospheric pressure, and then quenched in iced water. The structure and composition of phases were determined using microstructural, X-ray diffraction, and X-ray energy dispersive analyses. The maximum solubility of zinc was found to be 5·3 wt-% in FeAl₃, 20·9 wt-% in Fe₂Al₅, and 2·0 wt-% in FeAl at 450°C. Based on these results, an isothermal section for the aluminium rich corner of the Fe–Al–Zn ternary phase diagram is proposed.

MST/1196     

Experimental assessment of the Ru–Al–Ni ternary phase diagram at 1000 and 1100 °C

Knowledge of phase equilibria in the Ru–Al–Ni ternary system is relevant to the development of new single crystal Ni-based superalloys as well as to new high temperature protective coating systems for these alloys. A series of diffusion couple investigations have been performed across the Ru–Al–Ni ternary system in order to establish phase fields and possible diffusion paths. A continuous B2 phase has been shown to exist across the Ru–Al–Ni ternary between the RuAl and NiAl phases at temperatures of 1000 and 1100 °C. Ternary isothermal sections for Ru–Al–Ni at 1000 and 1100 °C are presented.     

Experimental investigation and thermodynamic calculation of Bi–Ga–Sb phase diagram

Abstract

Phase diagram of the Bi–Ga–Sb ternary system has been investigated by DTA and SEM with EDS measurements. Phase transition temperatures in four vertical sections and isothermal section at 500°C were studied. Experimental results were compared with calculated phase diagram by the Calphad method.