Design criteria for high-temperature steels strengthened with vanadium nitride

Fe-8-12Cr ferritomartensitic steels are widely used in the power generation, petrochemical and nuclear industries where they are subject to high operating temperatures and stresses. Resistance to creep deformation is therefore a critical materials property. One method of providing creep resistance is to precipitate a fine homogeneous distribution of vanadium nitride (VN) particles in the matrix. Maximizing this precipitation hardening effect requires a high nitrogen content, but this could cause gas bubble formation during conventional fabrication processes. It is therefore necessary to determine how much N can be added without encountering such problems. Phase stability calculations, using Thermo-Calc, were carried out to find high-N compositions to optimize the fraction of VN and the fabrication route for obtaining fine particles. Several experimental compositions, including nine high-nitrogen alloys, were fabricated as ingots; out of these, two exhibited porosity Thermo-Calc predicts that, in all of the high-nitrogen alloys, nitrogen gas is a stable phase around the solidus temperature. It is evident that porosity cannot simply be predicted from the presence of the gas phase on the equilibrium diagram. However, detailed analysis of the equilibrium phases predicted in these alloys, including their variation with composition, allowed a porosity criterion to be obtained. This criterion links porosity formation to the nature of the liquid-to-solid transformation. Further calculations were carried out to predict the dependence of gas phase evolution on both composition and pressure. Thermodynamic calculations are a valuable tool for the design of these industrially important alloys. Input from experimental data has enabled the refinement of the initial design criteria such that it should now be possible to propose compositions with high VN hardening but without the risk of porosity. This paper was presented at the International Symposium on User Aspects of Phase Diagrams, Materials Solutions Conference and Exposition. Columbus, Ohio, 18–20 October, 2004.     

Thermodynamic study of the phase equilibria in the Sn−Ti−Zn ternary system

The Sn−Ti−Zn ternary phase diagram has been constructed using the CALPHAD technique. The Ti−Zn binary system phase boundaries were determined using differential scanning calorimetry and the solid-liquid diffusion couples method. In addition, the formation energy of some stoichiometric compounds was obtained using first-principle band energy calculations. For the ternary system, some alloys were prepared by equilibration at 600 or 700 °C, and the compositions of the precipitates were analyzed using electron probe microanalysis. Thermodynamic assessment of the Ti−Zn and Sn−Ti−Zn systems was performed based on the experimental information and by adopting reported values of the thermodynamic properties of the Sn−Zn and Sn−Ti binary systems. Microstructural observation showed that Sn₃Ti₅Zn₁₂ exists in the ternary system. Seven types of invariant reaction on the Sn-rich liquidus surface of the ternary system are predicted by the phase diagram calculations. The ternary eutectic point falls at 0,0009 mass% Ti and 8.69 mass% Zn, at T=192.40°C, which is slightly lower than the calculated eutectic point of Sn−Zn binary alloy (T=192.41°C). Based on these results, a nonequilibrium solidification process using the Scheil model was simulated. This paper was presented at the International Symposium on User Aspects of Phase Diagrams, Materials Solutions Conference and Exposition, Columbus, Ohio, 18–20 October, 2004.     

Computer-assisted optimization of cobalt-base alloy compositions

Cobalt-base hard metals are known for their wear and corrosion resistance and also for their ability to retain hardness at elevated temperatures.

Considering the matrix of these alloys it can be predicted that (a) the performance against corrosive media will improve when the Cr content is increased, (b) a higher W content will be advantageous because of its solid solution strengthening effect, and (c) care has to be taken in the course of liquid phase sintering to avoid unwished-for carbides and/or intermetallic phases, because these would be detrimental with respect to mechanical properties of the alloys.

To locate ranges for optimal matrix and carbide compositions thermodynamic calculations with were carried out on the basis of recently published data which were improved by a new optimization routine.

A series of phase diagrams was calculated and the optimal compositions of alloys were derived. Furthermore, calculated transition temperatures and phase compositions of some selected alloys compare reasonably with published experimental results.     

Experimental Investigation of Microstructure and Phase Transitions in Ag-Cu-Zn Brazing Alloys

Microstructure and phase transitions of selected brazing alloys from the Ag-Cu-Zn ternary system were investigated. Four ternary alloys with silver content in the compositional range from 25 to 60 wt.% were studied using x-ray diffraction (XRD) and scanning electron microscopy coupled with the energy-dispersive spectroscopy (SEM–EDS). Phase transitions of the investigated alloys were measured using differential scanning calorimetry (DSC). Experimentally obtained results were compared with the results of a thermodynamic calculation of the phase equilibria according to the CALPHAD method. The experiments confirmed the optimized thermodynamic parameters for the calculations from the thermodynamic assessment in literature. Phase compositions, liquidus and solidus temperatures were confirmed by the EDS and DTA methods. Additionally, the calculated solidification paths and predicted phase transformations were in agreement with the SEM images.     

A figure of merit for predicted phase diagrams

A figure of merit is proposed that can be used to evaluate the accuracy of a predicted diagram. The figure of merit is the“probability that a phase will be predicted correctly” in a randomly selected alloy. The figure of merit depends on both the phase and the boundaries of the phase diagram being considered. It can be determined in two ways, either by the use of ZPF (zero phase fraction) lines or from the results of phase analyses on selected alloys. This paper was presented at the International Phase Diagram Prediction Symposium sponsored by the ASM/MSD Thermodynamics and Phase Equilibria Committee at Materials week, October 21–23,1991, in Cincinnati, OH. The symposium was organized by John Morral, University of Connecticut, and Philip Nash, Illinois Institute of Technology.     

A figure of merit for predicted phase diagrams

A figure of merit is proposed that can be used to evaluate the accuracy of a predicted diagram. The figure of merit is the“probability that a phase will be predicted correctly” in a randomly selected alloy. The figure of merit depends on both the phase and the boundaries of the phase diagram being considered. It can be determined in two ways, either by the use of ZPF (zero phase fraction) lines or from the results of phase analyses on selected alloys. This paper was presented at the International Phase Diagram Prediction Symposium sponsored by the ASM/MSD Thermodynamics and Phase Equilibria Committee at Materials week, October 21–23,1991, in Cincinnati, OH. The symposium was organized by John Morral, University of Connecticut, and Philip Nash, Illinois Institute of Technology.     

The ternary Gd-Li-Mg system: Phase diagram study and computational evaluation

The binary Gd-Li and the ternary Gd-Li-Mg systems were studied experimentally by thermal analysis and phase equilibration and also by thermodynamic calculations using the CALPHAD method. Ternary phase equilibria at 250 °C were studied with 55 different alloys that were annealed for 400 h and analyzed by x-ray diffractometry. A thermodynamic assessment of the binary Gd-Li system was also performed and the calculated phase diagram is presented. In the Gd-Li-Mg system, ternary solubilities of Li in GdMg (up to 5 at.% Li), GdMg₂ (up to approximately 3 at.% Li), and GdMg₃ (up to 5 at.% Li) were found at 250 °C. No ternary compound was observed. Lattice parameters for different compositions are given for these phases. Thermal analysis using a ternary key sample of composition near the invariant reaction L′=L+(βGd)+GdMg provided the data that were needed to determine a thermodynamic parameter for the ternary liquid. Thermodynamic data sets for the ternary solid solution phases were also developed. Based on the present data sets and those of the binary Gd-Mg and Li-Mg systems from the literature, the phase equilibria in the entire ternary system were calculated. Isothermal and vertical sections of the phase diagram and the projection of the liquidus surface are shown. These calculated phase diagrams are well supported by the experimental data.     

The ternary Gd-Li-Mg system: Phase diagram study and computational evaluation

The binary Gd-Li and the ternary Gd-Li-Mg systems were studied experimentally by thermal analysis and phase equilibration and also by thermodynamic calculations using the CALPHAD method. Ternary phase equilibria at 250 °C were studied with 55 different alloys that were annealed for 400 h and analyzed by x-ray diffractometry. A thermodynamic assessment of the binary Gd-Li system was also performed and the calculated phase diagram is presented. In the Gd-Li-Mg system, ternary solubilities of Li in GdMg (up to 5 at.% Li), GdMg₂ (up to approximately 3 at.% Li), and GdMg₃ (up to 5 at.% Li) were found at 250 °C. No ternary compound was observed. Lattice parameters for different compositions are given for these phases. Thermal analysis using a ternary key sample of composition near the invariant reaction L′=L+(βGd)+GdMg provided the data that were needed to determine a thermodynamic parameter for the ternary liquid. Thermodynamic data sets for the ternary solid solution phases were also developed. Based on the present data sets and those of the binary Gd-Mg and Li-Mg systems from the literature, the phase equilibria in the entire ternary system were calculated. Isothermal and vertical sections of the phase diagram and the projection of the liquidus surface are shown. These calculated phase diagrams are well supported by the experimental data.     

Theoretical study of phase stability in Ni-Al and Ni-Ti alloys

The thermodynamic stability of the bcc and fcc based ordered phases in Ni-Ti and Ni-AI has been studied with a highly accurate first-principles electronic structure method. The occurrence of a martensitic transformation in Ni-AlB2 ordered intermetallic alloys is discussed with relation to the existence of intermediate structures between bcc and fcc based phases. It is shown that closely related ordered structures can exist on fcc and bcc lattices in the composition range where the transformation occurs. The Ni-rich side of the Ni-Al phase diagram has been computed, and a comparison with a recent assessment is made. In addition, the rather unusual appearance of the NiTi B2 ordered structure in the phase diagram is discussed. This paper was presented at the International Phase Diagram Prediction Symposium sponsored by the ASM/MSD Thermodynamics and Phase Equilibria Committee at Materials Week, October 21–23,1991, in Cincinnati, Ohio. This symposium was organized by John Morral, University of Connecticut, and Philip Nash, Illinois Institute of Technology.     

Theoretical study of phase stability in Ni-Al and Ni-Ti alloys

The thermodynamic stability of the bcc and fcc based ordered phases in Ni-Ti and Ni-AI has been studied with a highly accurate first-principles electronic structure method. The occurrence of a martensitic transformation in Ni-AlB2 ordered intermetallic alloys is discussed with relation to the existence of intermediate structures between bcc and fcc based phases. It is shown that closely related ordered structures can exist on fcc and bcc lattices in the composition range where the transformation occurs. The Ni-rich side of the Ni-Al phase diagram has been computed, and a comparison with a recent assessment is made. In addition, the rather unusual appearance of the NiTi B2 ordered structure in the phase diagram is discussed. This paper was presented at the International Phase Diagram Prediction Symposium sponsored by the ASM/MSD Thermodynamics and Phase Equilibria Committee at Materials Week, October 21–23,1991, in Cincinnati, Ohio. This symposium was organized by John Morral, University of Connecticut, and Philip Nash, Illinois Institute of Technology.     

High-temperature phase equilibria in Cr-Cr3Si two-phase alloys

Phase equilibria in two-phase Cr-Cr₃Si alloys have been investigated using metallography, XRD, and electron microprobe analysis. Cr-Si alloys with compositions of up to 15.0% Si were directionally solidified using cold crucible Czochralski crystal growth and equilibrated chemically at either 1200,1400, or 1600 °C. Measured Si concentrations of the Cr and the Cr₃Si phases were found to be significantly lower than those given by the most recent assessment of the Cr-Si phase diagram, particularly at temperatures above 1200 °C. This explains why the volume fraction of Cr₃Si in the directionally solidified eutectic is lower than that predicted by the assessed phase diagram. X-ray lattice parameter data for both Cr and Cr₃Si are also reported.     

High-temperature phase equilibria in Cr-Cr3Si two-phase alloys

Phase equilibria in two-phase Cr-Cr₃Si alloys have been investigated using metallography, XRD, and electron microprobe analysis. Cr-Si alloys with compositions of up to 15.0% Si were directionally solidified using cold crucible Czochralski crystal growth and equilibrated chemically at either 1200,1400, or 1600 °C. Measured Si concentrations of the Cr and the Cr₃Si phases were found to be significantly lower than those given by the most recent assessment of the Cr-Si phase diagram, particularly at temperatures above 1200 °C. This explains why the volume fraction of Cr₃Si in the directionally solidified eutectic is lower than that predicted by the assessed phase diagram. X-ray lattice parameter data for both Cr and Cr₃Si are also reported.     

Measurements of liquidus temperatures in the Cu-Nb and Cu-Cr systems

The Cu-Nb and Cu-Cr alloys at compositions ranging from 5 to 86 wt% Nb (89 wt% Cr) were processed in a clean environment and solidified at relatively low cooling rates of 50 to 75 °C/s to determine liquidus temperatures. In this study, both temperature measurements and microstructural observations confirmed the equilibrium phase diagram having an S-shaped, nearly flat liquidus, rather than that with a monotectic reaction in the liquid state. However, a metastable liquid miscibility gap exists in the two systems.     

Phase constitution of some intermetallics in continuous quaternary pillar phase diagrams

In order to express multicomponent phase relationships, a new type of phase diagram, named a “pillar phase diagram,” is proposed. The pillar phase diagram is a sort of quaternary and Brewertype phase diagram. A pillar phase diagram at a temperature is easily constructed by (1) composing three sides of Brewer-type ternary-phase diagrams along the periodic table and (2) piling triangles of general ternary phase diagrams along the periodic table. Using the pillar phase diagrams, systematic understandings of phase constitution and stability along the periodic table can be performed for (1) binary intermetallics containing ternary and quaternary additional elements and (2) ternary intermetallics containing quaternary elements. Thus, the diagrams are convenient in terms of alloy design of multiphase intermetallic alloys. In this paper, the concept and the construction method of the pillar phase diagrams are described, and some examples are shown for systems related with L1₂ Ni₃Al, B2 NiAl, L2₁ Ni₂AlTi, B2 NiTi, B2 FeTi, L1₀ TiAl, and L1₂ Al₃Ti alloys.     

Phase constitution of some intermetallics in continuous quaternary pillar phase diagrams

In order to express multicomponent phase relationships, a new type of phase diagram, named a “pillar phase diagram,” is proposed. The pillar phase diagram is a sort of quaternary and Brewertype phase diagram. A pillar phase diagram at a temperature is easily constructed by (1) composing three sides of Brewer-type ternary-phase diagrams along the periodic table and (2) piling triangles of general ternary phase diagrams along the periodic table. Using the pillar phase diagrams, systematic understandings of phase constitution and stability along the periodic table can be performed for (1) binary intermetallics containing ternary and quaternary additional elements and (2) ternary intermetallics containing quaternary elements. Thus, the diagrams are convenient in terms of alloy design of multiphase intermetallic alloys. In this paper, the concept and the construction method of the pillar phase diagrams are described, and some examples are shown for systems related with L1₂ Ni₃Al, B2 NiAl, L2₁ Ni₂AlTi, B2 NiTi, B2 FeTi, L1₀ TiAl, and L1₂ Al₃Ti alloys.     

Phase diagram modeling for titanium alloys with light element impurities

It is well known that low levels of light element impurities, such as oxygen and nitrogen, can significantly modify phase equilibria in conventional titanium alloys. However, although the role of nitrogen and oxygen as alpha stabilizers is well established, little quantitative work exists in ternary and higher order systems. Moreover the effect of such elements on equilibria with phases other than cx-and P-Ti is often unknown. The problems in measuring light elements at the microscopic level adds to the difficulty of establishing partitioning, and old axioms are often transferred to new alloys with little evidence that they are applicable. As part of a current program on titanium alloys, phase diagram modeling has been performed for a variety of titanium alloys with additions of oxygen and nitrogen. This paper presents results for the system Ti-Al-V-O-(N,C) with particular reference to the O additions to the commercially important alloy Ti-6A1-4V. This paper was presented at the International Phase Diagram Prediction Symposium sponsored by the ASM/MSD Thermodynamics and Phase Equilibria Committee at Materials Week, October 21–23,1991, in Cincinnati, OH. The symposium was organized by John Morral, University of Connecticut, and Philip Nash, Illinois Institute of Technology.     

Phase diagram modeling for titanium alloys with light element impurities

It is well known that low levels of light element impurities, such as oxygen and nitrogen, can significantly modify phase equilibria in conventional titanium alloys. However, although the role of nitrogen and oxygen as alpha stabilizers is well established, little quantitative work exists in ternary and higher order systems. Moreover the effect of such elements on equilibria with phases other than cx-and P-Ti is often unknown. The problems in measuring light elements at the microscopic level adds to the difficulty of establishing partitioning, and old axioms are often transferred to new alloys with little evidence that they are applicable. As part of a current program on titanium alloys, phase diagram modeling has been performed for a variety of titanium alloys with additions of oxygen and nitrogen. This paper presents results for the system Ti-Al-V-O-(N,C) with particular reference to the O additions to the commercially important alloy Ti-6A1-4V. This paper was presented at the International Phase Diagram Prediction Symposium sponsored by the ASM/MSD Thermodynamics and Phase Equilibria Committee at Materials Week, October 21–23,1991, in Cincinnati, OH. The symposium was organized by John Morral, University of Connecticut, and Philip Nash, Illinois Institute of Technology.     

The Pb−Sn (Lead-Tin) system

This system was analyzed using computer-coupled phase diagram/thermodynamic computational procedure. The calculations were performed with the F^*A^*C^*T on-line computing system. The work was partially supported by a grant from the Canadian National Committee of the ASM/NBS Phase Diagram Program. Literature searched through 1986. Dr. Thompson is the ASM/NBS Data Program Co-Category Editor for binary silver alloys.     

Thermodynamic evaluation of the phase equilibria and glass-forming ability of the Ti−Be system

The glass-forming ability of Ti−Be alloys is of great interest. Experimental and theoretical evaluations of the glass-forming ability of this binary alloy show that the formation of a metastable TiBe phase with a CsCl-type B2 structure controls the glass-forming ability in this system. However, there is no information on the thermochemical properties of metastable TiBe for the quantitative evaluation of the glass-forming ability using Davies-Uhlmann kinetic formulations. We have carried out a thermodynamic analysis using experimental phase diagram data and the energy of formation of the stoichiometric compounds from ab initio calculations. Furthermore, the Gibbs energy of formation for the body-centered cubic (bcc) phase was evaluated over the entire composition range by applying the cluster expansion method (CEM) to the total energy of some bcc-based ordered structures obtained from ab initio calculations. For the bcc phase, the two-sublattice formalism, (Ti, Be)_0.5(Ti,Be)_0.5, was adopted to describe the A2/B2 transformation. A good agreement between the calculated values and experimental phase equilibria was obtained. Evaluation of the glass-forming ability was also attempted utilizing the thermodynamic quantities obtained from the phase diagram assessment. The calculated glass-forming ability agrees well with the experimental results. This paper was presented at the International Symposium on User Aspects of Phase Diagrams, Materials Solutions Conference and Exposition. Columbus, Ohio, 18–20 October, 2004.     

Measurements of liquidus temperatures in the Cu-Nb and Cu-Cr systems

The Cu-Nb and Cu-Cr alloys at compositions ranging from 5 to 86 wt% Nb (89 wt% Cr) were processed in a clean environment and solidified at relatively low cooling rates of 50 to 75 °C/s to determine liquidus temperatures. In this study, both temperature measurements and microstructural observations confirmed the equilibrium phase diagram having an S-shaped, nearly flat liquidus, rather than that with a monotectic reaction in the liquid state. However, a metastable liquid miscibility gap exists in the two systems.