Melting equilibria in the iron-rich corner of the Fe-Ni-Cr system

Isothermal holding tests were carried out on the Fe-Ni-Cr system in the two-phase region between the melt and crystal in order to determine the γ and δ liquidus surfaces in the iron-rich corner, to establish the position of the peritectic line running between them, and to compare the results with those contained in relevant literature. The initial contents of the 13 test series were staggered in roughly equal intervals from 29.6% Ni and 12.9% Cr to 18.7% Ni and 28.4% Cr. They were held between the temperatures of 1450 and 1530 °C at intervals of 10 °C for 40 minutes in each case, so that 93 liquidus concentrations and temperatures were determined. Both liquidus surfaces can be described very accurately with corresponding mathematical equations and mathematically intersected in order to determine the course of the peritectic line. The results enable sufficiently accurate development of the melting equilibria of the entire ternary system, building on the basis provided by the known γ and δ liquidus lines of the three binary systems.     

Phase equilibria in Al-rich Al-Sc-Cr alloys

Phase equilibria in aluminum alloys containing up to 1.2 wt % Sc and 1.0 wt % Cr are studied by optical microscopy and differential thermal and electron microprobe analyses. Two vertical sections and the projection of liquidus surface have been constructed. The four-phase nonvariant equilibrium at a temperature of 656.5 ± 1°C is found to have a transition character. The Al-based solid solution is found to be in equilibrium only with the Al₃Sc and Al₇Cr binary phases.     

Melting equilibria in the iron-rich corner of the Fe-Ni-Mo system

Isothermal holding tests were carried out in the Fe-Ni-Mo system in the two-phase region between the liquidus (melt) and the solidus (crystal). The δ and γ liquidus surfaces in the iron-rich corner of the Fe-Ni-Fe₃Mo₂-NiMo subsystem, as well as the position of the peritectic line situated between them, could be very accurately established by the experimentally determined isotherms. Based on these results and on the known liquidus lines in the three boundary binary systems, as well as on the known concentration fields of the Fe₃Mo₂-NiMo solid solutions, the melting equilibria could be developed with sufficient accuracy in the entire subsystem.     

Phase equilibria in the titanium corner of hypoeutectic alloys in the Ti-Nb-Si-Al system

Physicochemical analysis methods have been applied to the phase equilibria in the Ti-Nb-Si-Al system in the region of alloys rich in titanium. It is found that the crystallization conditions for hypoeutectic alloys with constant 5 at.% aluminum content control the niobium contents up to 17.5 at.%, for which there are two groups. After the primary crystallization of the β phase in alloys in these groups, binary eutectics are formed with different intermetallic phases. The properties of the alloys are dependent on the phase compositions in the eutectic mixtures. The temperature and concentration stability of the phases have been determined. It is shown that a peritectic reaction may give rise to a second intermetallide phase in alloys approximating to equilibrium as a result of subsequent annealing, which does not affect the structure of the cast alloys.     

Thermodynamics and phase equilibria in the Al-In-Sb system

As part of a program for determination of the thermodynamic properties of the group III and V alloys and assessment of the phase equilibria, the activities of aluminum in the liquid Al-In-Sb system have been measured using a concentration cell of the type

Solidification and phase equilibria in the Fe-C-Cr-NbC system

A solidification model is developed and experimentally checked for Fe-C-Cr-Nb alloys in the white cast irons range. It is based on a partial quaternary Fe-C-Cr-NbC phase diagram and predicts the possible solidification paths for the alloys containing γ, with (Fe,Cr)₇C₃ and NbC as the microconstituents at room temperature. The dendritic γ to massive (Fe,Cr)₇C₃ transition in experimental alloy microstructures with NbC contents up to 22 pet is explained by this model. Thermal analysis is also used to compare the solidification paths and model approach.     

Thermodynamic computation of phase equilibria in the sodium-carbon-oxygen system

An existing computational technique was adapted for the derivation of ternary constitution diagrams in the sodium-carbon-oxygen system. The method involved the selection of appropriate chemical equations among seven condensed phases including sodium, carbon, Na₂C₂, Na₂CO₃, Na₂O, Na₂O₂, NaO₂ and the three gases CO, CO₂ and sodium vapor. Using available thermochemical data, gas partial pressures were computed and ternary isotherms derived. At temperatures near 750°C and 1 atm pressure, carbon and Na₂CO₃ can coexist with liquid sodium at high carbon-oxygen ratios whereas carbon and Na₂CO₃ can coexist at low carbon-oxygen ratios. At somewhat higher temperatures and pressures, Na₂C₂ may be an important phase. Although solubility effects would alter slightly the computed data, the results of the study generally agree with the experimental observations of others. ANDREW B. WEAVER, formerly Graduate Student, University of Nebraska.     

High-temperature phase relations and thermodynamics in the silver-tin-sulfur system

The SnS activities in liquid Ag₂S-SnS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid matte solutions were modeled by the Wilson equations. Part of the liquid boundaries of the Ag₂S-SnS phase diagram were derived from the model equations, yielding a eutectic temperature of 528 °C at x _SnS=0.38. The phase diagram of the pseudobinary Ag₂S-SnS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. Solubility limits of the components at the narrow-terminal solid-solution ranges were determined around the eutectic temperature. Within the Ag-Sn-S ternary system, the boundaries of the immiscibility region, together with the tie-line distributions, were established at 1200 °C. Activities of Ag, Sn, and S along the miscibility gap were calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.     

Al-rich portion of the Al-Hf phase diagram

Electrical resistivity measurements, differential thermal analysis, optical microscopy, and the deposition of hafnium compound particles from a melt are used to study the Al-rich portion of the Al-Hf phase diagram. Prominence is given to the hafnium solubility in solid and liquid aluminum. The studies show a peritectic character of the invariant reaction during the solidification of alloys with sufficiently high hafnium contents and a slight difference between the peritectic and melting temperatures of pure aluminum. The hafnium solubility in solid and liquid aluminum is shown to increase with the temperature. The hafnium solubility in solid aluminum at the peritectic temperature (maximum solubility) is 1.00 wt % (0.153 at %); the hafnium solubility in liquid aluminum at this temperature is 0.43 wt % (0.065 at %).     

High-temperature phase relations and thermodynamics in the iron-titanium-oxygen system

Phase equilibria and thermodynamics in the FeO-TiO₂-Ti₂O₃ ternary system were studied at 1500 °C and 1600 °C. In particular, the liquid slag-phase region and its saturation boundary with respect to metallic iron, titania, and lower titanium oxides was investigated. The liquid slag-phase region extends substantially toward an anosovite (Ti₃O₅) composition, and considerable concentrations of divalent iron coexist with trivalent titanium in the liquid-slag phase. This seems to be a consequence of the complete solid solution between ferrous pseudobrookite (FeTi₂O₅) and anosovite (Ti₃O₅), which exists at subsolidus temperatures. The liquid-slag field is significantly enlarged toward the anosovite composition upon increasing the temperature from 1500 °C to 1600 °C. Activities of the components “FeO” and TiO₂ in the liquid-slag region were determined by Gibbs-Duhem integration of the measured oxygen partial pressures at 1500 °C. The FeO shows moderate negative deviation, while titania shows a slight negative deviation in FeO-rich slags and a positive deviation in high-titania slags. The experimentally measured activity values were modeled using regular and biregular solution models, and good agreement was obtained with the biregular solution model.     

High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C atX _Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.     

Experimental study of the phase equilibria in the Fe-Mn-Al system

The isothermal sections with lower Al content at 800 ‡C, 900 ‡C, 1200 ‡C, and 1300 ‡C and two vertical sections of 4 wt pct Al and 8 wt pct Al in the Fe-Mn-AI system were determined by means of the diffusion couple technique, metallographic method, and differential thermal analysis (DTA). It is shown that the results of isothermal and vertical sections coincide with each other, and the twophase (α + γ) region and three-phase (α + γ + β) region trend toward the Fe-Mn side and Mn corner with the rise of temperature, respectively. The experimental results are in agreement with those calculated by the present authors. Formerly Graduate Student, Department of Materials Science and Engineering, Northeastern University     

Investigation of the phase equilibria in the Sn-Bi-In alloy system

This article presents an investigation of the phase equilibria in the Sn-Bi-In ternary alloy system, performed both by theoretical and experimental methods. Following the regular solution model and a standard thermochemical calculation, a theoretical evaluation of the phase equilibrium in the entire ternary system is conducted. The thermodynamic parameters required for the calculation are initially obtained by fitting the model to existing data available from prior studies. The theoretical results are then validated and further improved by experimental work in which alloys with several critical compositions were chosen and examined. In the experimental work, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and energy-dispersive X-ray (EDX) spectroscopy were jointly used to identify the transition temperatures and the phases in the microstructure. The resulting phase diagram agrees well both with the existing data and with the data from the current experiments. However, different from previous findings, this study finds a nonbinary nature of the Sn-BiIn and Sn-BiIn₂ quasi-binaries and nine invariant reactions, one eutectic, six peritectic and two peritectoid. The phase-reaction scheme (Scheil diagram), the liquidus projection, and the phase diagram, covering entire compositional ranges, are established.     

Directional solidification and phase equilibria in the Ni-Al system

A method for the optimization of a phase diagram on the basis of results from directional solidification experiments is proposed. The experimental microstructure selection map is compared with a calculated map and the input parameters are varied until a satisfactory agreement is obtained. The calculation of the microstructure selection map is based on the maximum temperature criterion and on analytical models for the growth of plane front, dendritic, and eutectic structures. This method is applied to the Ni-Al system where the phase equilibria close to the melting point of the γ′-Ni₃Al phase have been subject to discussion for over 50 years. A new version of this part of the phase diagram is proposed, which is coherent with the results from directional solidification experiments.     

Stable and metastable phase equilibria in the Al-Mn system

The aim of the present investigation was resolution of certain obscure features of the Al-Mn phase diagram. The experimental approach was guided by assessment of the previous literature and modeling of the thermodynamics of the system. It has been shown that two phases of approximate stoichiometry “Al₄Mn” (λ and μ) are present in stable equilibrium, λ forming by a peritectoid reaction at 693 ± 2 °C. The liquidus and stable equilibrium invariant reactions as proposed by Goedecke and Koester have been verified. A map has been made of the successive nonequilibrium phase transformations of as-splat-quenched alloys. Finally, the thermodynamic calculation of the phase diagram allows interpretation of complex reaction sequences during cooling in terms of a catalogue of all the metastable invariant reactions involving (Al), Al₆Mn, λ, μ, ?, and Al₁₁Mn₄ phases.