Phase relationships in the Fe-Cr-C system at solidification temperatures

The phase relationships between the liquid phase and the primary solid phases were investigated in the iron-rich corner of the Fe-Cr-C system. The investigation consisted of measurements of tie-lines and the liquidus surface of the liquid-delta (bcc) and liquid-gamma (fcc) equilibria in the Gibbs triangle, bounded by 0 to 1.4 wt pct C and 0 to 25 wt pct Cr (bal. Fe). The peritectic surface of the three-phase equilibrium was also measured. The temperature ranged from 1811 to about 1750 K. The tie-lines were obtained from liquid-solid equilibrium couples, and the liquidus and peritectic surfaces, by differential thermal analysis (DTA). A statistical procedure was applied to determine from the experimental results the parameters required for a thermodynamic model of the system. Calculations by the model are in good agreement with the experimental results. As a consequence the model can be used to interpolate and extrapolate properties and compositions of phases in equilibrium in the system within the composition and temperature field investigated. D.M. KUNDRAT, formerly Research Fellow at Massachusetts Institute of Technology M. CHOCHOL, formerly Research Assistant, Massachusetts Institute of Technology     

Phase relationships in the fe-cr-mn-ni-c system at solidification temperatures

The phase relationships between the liquid phase and the primary solid phases were investigated in the iron-rich corner of the quinary system Fe-Cr-Mn-Ni-C. Of the five quaternary systems that comprise the quinary system, this study was limited to the three quaternary systems which contain both carbon and iron as two of the components;viz.: Fe-Cr-Mn-C, Fe-Cr-Ni-C, and Fe-Mn-Ni-C, as well as all of the binary and ternary subsystems that have iron as a component. This paper discusses the modeling efforts for these systems, with particular emphasis on the ternary systems Fe-Cr-Mn and Fe-Mn-Ni and the quaternary systems Fe-Cr-Mn-C and Fe-Mn-Ni-C. The experimental investigation consisted of measurements of tie-lines for the liquid-delta (bcc) and the liquid-gamma (fcc) equilibria in the iron-rich corner of the Gibbs simplex bounded by 0 to 25 wt pct Cr, 0 to 12 wt pct Mn, 0 to 25 wt pct Ni, and 0 to 1.2 wt pct C (bal. Fe). The temperature ranged from 1811 to about 1750 K. Compositions for the tie-lines were obtained from liquid-solid equilibrium couples, and the temperatures for the equilibrium by differential thermal analysis (DTA). Parameters were selected in a thermodynamic model of the alloy system to minimize the square of the difference between experimentally and calculated tie-lines, the latter being implicitly a function of the derived parameters in the model. Binary and higher-order parameters were generally required. Ternary parameters were obtained on ironcarbon base alloys Fe-Cr-C, Fe-Mn-C, and Fe-Ni-C, and for the Fe-Cr-Ni system, but not for the Fe-Cr-Mn and Fe-Mn-Ni systems. Of the quaternary systems investigated, quaternary parameters were required only for theL/δ equilibrium in the Fe-Cr-Ni-C system; the Fe-Cr-Mn-C and Fe-Mn-Ni-C systems were found to be represented adequately by employing only binary and ternary parameters.     

Phase relationships in the Fe-Cr-Ni system at solidification temperatures

The phase relationships between the liquid phase and the primary solid phases were investigated in the iron-rich corner of the Fe-Cr-Ni system as part of a larger study of the Fe-Cr-Ni-C system. The investigation consisted of measurements and modeling of tie-lines and the liquidus surfaces of the liquid-delta (bcc) and liquid-gamma (fcc) equilibria and the peritectic surface involving all three phases in the iron-rich corner of the Gibbs triangle bounded by 0 to 25 wt pct Cr and 0 to 25 wt pct Ni (bal Fe). The temperature ranged from the melting point of iron (1811 K) to about 1750 K. Compositions for tie-lines were obtained from liquid-solid equilibrium couples and temperatures for the surfaces were obtained by differential thermal analysis. Parameters for modeling the system were then selected in the subregular solution model to minimize the square of the difference between experimental and calculated tie-lines. With one ternary parameter employed for each phase, calculations by the model are in excellent agreement with the tie-line and liquidus measurements and in fair agreement with the temperatures for the peritectic surfaceL + δ/L + δ + γ. The usefulness of the model is demonstrated by calculation of the solidification paths of selected alloys in the composition field investigated for the limiting cases of (a) complete equilibrium followed by the alloy system, and (b) no solid diffusion (i.e., segregation) with equilibrium maintained at the solidifying front and complete mixing in the liquid phase.     

Determination of the Fe-rich portion of the Fe-Ni-C phase diagram

The iron-rich portion of the Fe-Ni-C phase diagram has been determined in the composi-tion range from 0 to 20 wt pct Ni and 0 to 6.67 wt pct C for four temperatures, 773, 873, 923 and 1003 K. Long term heat treatments were used to grow the ferrite plus austenite assemblages, while slow cooling heat treatments (25 K/h) were used to grow the metal plus carbide assemblages. Other types of heat treatments produced metal plus graphite. The two phase tie-lines and three phase tie-triangles were measured using electron mi-croprobe techniques. In samples where bulk equilibration had not been achieved, tie-lines were obtained by using extrapolated interface compositions, on the assumption of local equilibrium at the interface. The tie-lines lie at higher Ni contents than the equilibrium tie-line through the bulk composition. The tie-line shift was required to produce match-ing growth rates of Ni and C for the carbides. The addition of Ni slightly reduces the solubility of carbon in austenite and decreases the stability of the carbide phase. In addi-tion, the carbide is always Ni-poor relative to the coexisting metal phase(s).     

Thermodynamics of the iron-carbon-zinc system

A two-zone isopiestic experimental technique was used to determine the solubility of zinc vapor in liquid and solid iron-carbon alloys as a function of zinc partial pressure (0.1 to 1 atm), carbon content (0 to 4.6 wt Pct), and temperature (1473 to 1873 K). The solubility of zinc at a given partial pressure decreases with both increasing temperature and carbon content in both liquid alloys and solid austenite; its activity in these solutions, and in pure δ-ferrite, deviates more positively from ideality than previous model-based predictions have suggested. The Bale-Pelton unified interaction parameter formalism was successfully applied to the results of liquid-alloy experiments, but the degree of experimental scatter in the austenite equilibrations was too great to allow its application in the calculation of solid-solution iron-carbon-zinc thermodynamic parameters. Using the available results, values were calculated for the equilibrium partition coefficientK _zn in solidifying iron-carbon alloys as a function of alloy carbon content; the results suggest that significant segregation of zinc between solid and liquid phases is not likely.     

A process for debismuthizing lead with magnesium

Significant amounts of bismuth can be removed from magnesium-lead alloys by crystallization of the intermetallic compounds Mg_{0. 6573}Pb_{0. 3427} and Mg_0.662Pb_0.338in the Mg₂Pb, magnesium plumbide phase field of the Pb-Mg-Bi system. The results of the previous studies have been used to develop a process for debismuthizing lead using controlled conditions for the crystallization of magnesium plumbide from alloys containing 0.03 to 0.06 wt Pct bismuth and magnesium whose concentration is determined by the relationship wt Pct Mg = 2.9 + 20 x wt Pct Bi. A flow diagram showing the sequence of operations is presented together with a material balance, which was established from data obtained from individual experiments simulating the previously mentioned unit operations, with a final product containing less than 0.0010 wt Pct Bi. The process also includes the recycling of magnesium recovered by vacuum distillation. Additional procedures are included to extend the process to treat alloys containing up to 1.5 wt pct bismuth.     

Reduction of Chromite in Liquid Fe-Cr-C-Si Alloys

The kinetics and the mechanism of the reduction of chromite in Fe-Cr-C-Si alloys were studied in the temperature range of 1534 °C to 1702 °C under an inert argon atmosphere. The rotating cylinder technique was used. The melt consisted of 10 and 20 wt Pct chromium, the carbon content varied from 2.8 wt Pct to saturation, and the silicon content varied from 0 to 2 wt Pct. The rotational speed of the chromite cylinder ranged from 100 to 1000 rpm. The initial chromium to iron ratios of the melts varied between 0.11 and 0.26. In Fe-C melts, the effect of rotational speed on the reduction of chromite was very limited. Carbon saturation (5.4 wt Pct) of the alloy caused the reduction to increase 1.5 times over the reduction observed in the unsaturated (4.87 wt Pct) alloy at a given rotational speed. The addition of chromium to the carbon-saturated Fe-C alloy increased the reduction rate. The addition of silicon to the liquid phase increased the reduction rate drastically. The reduction of chromite in Fe-Cr-C melts is hindered because of the formation of, approximately, a 1.5-mm-thick M₇C₃-type carbide layer around the chromite cylinders. This carbide layer did not form when silicon was present in the melt. It was found that the reduction rate is controlled by the liquid-state mass transfer of oxygen. The calculated apparent activation energies for diffusion were 102.9 and 92.9 kJ/mol of oxygen in the Si-O and C-O systems, respectively.     

Morphological stability of α-β phase interfaces in the Cu−Zn−Ni system at 775°C

An experimental investigation into the morphological stability of α-β phase interfaces in the Cu−Zn−Ni system at 775°C has been undertaken. As a preliminary to this study, it was necessary to also determine certain significant diffusion and equilibrium parameters for the composition range of interest (35 to 50 wt pct Zn and 0 to 10 wt pct Ni). Using two-phase infinite diffusion couples, all with the same α terminal composition but with various β terminal compositions, the transition from a stable to an unstable planar α-β interface was indexed. The time evolution of unstable phase interfaces was also examined. The experimentally observed transition is in good agreement, with the transition which is predicted on the basis of linear perturbation theory.     

Decomposition of Fe-Ni martensite: Implications for the low-temperature (≤500 °C) Fe-Ni phase diagram

The low-temperature (<500 °C) decomposition of Fe-Ni martensite was studied by aging martensitic Fe-Ni alloys at temperatures between 300 °C and 450 °C and by measuring the composition of the matrix and precipitate phases using the analytical electron microscope (AEM). For aging treatments between 300 °C and 450 °C, lath martensite in 15 and 25 wt pct Ni alloys decomposed with γ [face-centered cubic (fcc)] precipitates forming intergranularly, and plate martensite in 30 wt pct Ni alloys decomposed with γ (fcc) precipitates forming intragranularly. The habit plane for the intragranular precipitates is {111}_fcc parallel to one of the {110}_bcc planes in the martensite. The compositions of the γ intergranular and intragranular precipitates lie between 48 and 58 wt pct Ni and generally increase in Ni content with decreasing aging temperature. Diffusion gradients are observed in the matrix α [body-centered cubic (bcc)] with decreasing Ni contents close to the martensite grain boundaries and matrix/precipitate boundaries. The Ni composition of the matrix α phase in decomposed martensite is significantly higher than the equilibrium value of 4 to 5 wt pct Ni, suggesting that precipitate growth in Fe-Ni martensite is partially interface reaction controlled at low temperatures (<500 °C). The results of the experimental studies modify the γ/α + γ phase boundary in the present low-temperature Fe-Ni phase diagram and establish the eutectoid reaction in the temperature range between 400 °C and 450 °C. Formerly Research Assistant, Department of Materials Science and Engineering, Lehigh University     

The kinetics of carbide precipitation in silicon-aluminum steels

The kinetics of carbide precipitation in a fully processed 2.3 wt Pct silicon, 0.66 wt Pct aluminum electrical steel with carbon contents of 0.005 to 0.016 wt Pct were investigated over the temperature range from 150 to 760 °C and times from 30 seconds to 240 hours. The size, morphology, and distribution of the carbide phases, as functions of aging time and temperature, were determined by optical and transmission electron microscopy. The 1.5T core loss was also evaluated and correlated with the changes in precipitation. Distinct C curves were observed for the formation of grain-boundary cementite at temperatures above 350 °C and a transition carbide ({100} _α habit plane) at temperatures below 350 °C. Grain-boundary cementite had a relatively small effect on core loss. The large increases in core loss that accompanied transition carbide precipitation peaked at specific aging temperatures depending on the carbon content of the steel. Once a transition carbide dispersion was initially established at a given aging temperature, particle coarsening and core loss changes were generally insensitive to aging time. The influence of a combined addition of silicon and aluminum on the solubility of cementite and the transition carbide in iron was estimated and discussed. This paper is based on a presentation made at the symposium “Physical Metallurgy of Electrical Steels” held at the 1985 annual AIME meeting in New York on February 24–28, 1985, under the auspices of the TMS Ferrous Metallurgy Committee.     

Thermodynamics and phase relationships of transition metal-sulfur systems: Part V. A reevaluation of the Fe-S system using an associated solution model for the liquid phase

The relevant thermodynamic and phase equilibrium data for the Fe-S binary system have been reevaluated in light of more recent data. An associated solution model is used to describe the thermodynamic properties of the liquid phase as a function of composition and temperature. For the pyrrhotite phase, a statistical thermodynamic model based on the formation of Frenkel defects in the lattice is used. For the austenite and ferrite phases, the solute is assumed to follow Henry’s law, and pyrite is taken to be a stoichiometric compound. The model parameters for the various phases are obtained by evaluating all relevant experimental data reported in the literature. The calculated phase diagram is in good agreement with the experimental data. The calculated sulfur activity values for the liquid phase agree well with experimental values including those at higher sulfur concentrations. This is an improvement of an earlier evaluation by Sharma and Chang using the same model with the same number of parameters.     

A Study of The Constitution of The Titanium-Rich Corner of The Titanium-Aluminum-Molybdenum System

Abstract

The constitution of the titanium-rich corner of the titanium-aluminum-molybdenum system, based on a 4–hour annealing time, has been investigated. Vacuum heat-treatment and metallography have been used to determine the β-transus on nine constant titanium sections of this system in the composition range of 0–25wt % molybdenum and 0–15 wt % aluminum. Using these sections, together with published data on the titanium-aluminum and titanium-molybdenum binary diagrams, isothermal sections at 850, 900, 950 and 990°C (1562, 1652, 1742 and 1814°F) have been developed and tie-lines have been determined for these sections. Four discontinuities in the β-transus surface have been discovered. These discontinuities appear to indicate the presence of four three-phase fields which are contiguous with two-phase fields in the titanium-aluminum binary diagram discovered by several other workers.     

Determination of the Fe−Ni phase diagram below 400°C

The phase diagram for the Fe−Ni system below 400°C has been determined experimentally in the composition range from 0 to 52 wt pct Ni using analytical electron microscopy techniques. High spatial resolution X-ray microanalysis and electron diffraction were conducted on the Fe−Ni regions of meteorites. Both stable and metastable phase boundaries were defined. Our phase diagram is consistent with the available theoretical diagram in that firm experimental evidence was found for a miscibility gap and an associated, asymmetrical spinodal decomposition region. The spinodal decomposition resulted in a two-phase, isotropic microstructure, as expected. The miscibility gap is a metastable construction arising from the presence of a tricritical point due to magnetic interactions. Our experimental diagram differs from the theoretical diagram in three ways. First, observations of meteorite structures show that Fe−Ni solid solution containing 4.0 wt pct Ni is in local equilibrium with ordered FeNi containing 51.4 wt pct Ni and not Ni₃Fe as in the theoretical diagram. Second, our miscibility gap below 400°C, located between 11.7 and 51.9 wt pct Ni at 200°C, is wider than the calculated miscribility gap, especially at the high Ni end. Third, we also find evidence for an ordered structure around ∼25 wt pct Ni. This structure may be either Fe₃Ni or a two-phase structure incorporating ordered FeNi.     

Spreading and interlayer formation at the copper-copper oxide/polycrystalline alumina interface

Spreadability and reaction layer growth rates of copper-oxygen alloys on polycrystalline alumina were measured above the melting point of copper to better understand the direct bonding process. Spreading was measured as a function of composition and temperature by monitoring the diameter of molten droplets as a function of time. As the oxygen content of the melt increased from 0 to 3 wt pct, the spreading diameter increased linearly, at fixed time and temperature. Constant diameters were observed for oxygen compositions between approximately 3 and 6 wt pct. The diameters again increased linearly for oxygen concentrations greater than 7 wt pct. This behavior was explained by reference to the copper-oxygen binary phase equilibrium. An interfacial product was identified to be the complex oxide, CuA10₂. A detailed investigation of the interlayer growth kinetics was performed to understand the fundamental phenomena controlling the spreading rates. The growth rate of the CuAlO₂ phase and the spreading rate were simultaneously measured for alumina in contact with a copper-2 wt pct oxygen alloy drop as a function of temperature. The reaction layer thickening was found to be diffusion controlled, with an apparent activation energy of 309 kJ/mol, and the spreading rate did not correlate with the thickening rate. Formerly Research Associate, Center for Welding and Joining Research, Department of Metallurgical and Materials Engineering     

Liquidus temperatures in calcium ferrite slags in equilibrium with molten copper

Experimental laboratory methods have been developed that enable phase-equilibria studies to be carried out on slags in the system Ca-Cu-Fe-O in equilibrium with metallic copper. These techniques involve equilibration at temperature, rapid quenching, and chemical analysis of the phases using electron-probe X-ray microanalysis (EPMA). Equilibration experiments have been carried out in the temperature range of 1150 °C to 1250 °C (1423 to 1523 K) and in the composition range of 4 to 80 wt pct “Cu₂O,” 0 to 25 wt pct CaO, and 20 to 75 wt pct “Fe₂O₃” in equilibrium with metallic copper. Liquidus and solidus data are reported for the primary-phase fields of spinel (magnetite) and dicalcium ferrite. The resulting data have been used to construct liquidus isotherms of the CaO-“Cu₂O”-“Fe₂O₃” system at metallic copper saturation.     

Processing of spent hydrorefining catalysts by selective chlorination

Spent hydrorefining catalysts may contain 4 to 6 Pct CoO and/or NiO, 8 to 16 Pct MoO₃, and up to 10 Pct V₂O₅, generally supported by alumina. Raw samples are roasted to eliminate C, S, and hydrocarbons contained in the spent catalysts. The optimum roasting temperature and time are 500 °C and 7 hours. Chlorination of roasted samples with Cl₂ + air, Cl₂ + N₂, and Cl₂ + CO is investigated in order to recover the valuable metals selectively. Depending on the chlorination parameters, it is possible to recover more than 80 Pct of the Ni and Co, about 95 Pct of the Mo, and up to 80 Pct of V compounds. The Co and Ni chlorides are obtained by leaching the chlorination residues with acidified water. The Mo and V chlorides and/or oxychlorides are obtained by selective condensation from the vapor phase. The chlorination of the catalyst support, A1₂O₃, can be limited to less than about 5 Pct. Besides the reaction temperature and time, the O₂ partial pressure of the chlorinating gas mixture appears to be the key factor for the reaction’s selectivity.     

The effect of continuous heating on the phase transformations in zinc- iron electrodeposited coatings

The crystal structure and phase transformations of electrodeposited zinc-iron coatings were investigated by several techniques. The phase composition of as-plated zinc-iron coatings was found to contain both 17 phase and8 phase and, according to the equilibrium phase diagram, was in a nonequilibrium condition for the compositions investigated. The transformation toward equilibrium during heating was a two-stage process. The first stage of transformation, at temperatures between 25 °C and 360 °C, is accomplished with very little change in composition, and the phase transformation occurs within the coating itself. It is proposed, through a simplified analysis, that the phase transformation in this stage is supported by short-range diffusion. In the second stage of the transformation, at temperatures above 360 °C, the iron content in the coating increases as a result of interdiffusion between the coating and the base steel, and the phase structure moves to the iron-rich side in accordance with the equilibrium phase diagram. MINGYUAN GU, formerly Visiting Research Scientist, Energy Research Center     

Transformations

Hot-dip galvanized drawing quality special killed (DQSK) steel and titanium stabilized interstitial free (IF) steel substrates were annealed under varying temperature and time conditions in order to characterize the coating structure development which occurs during the annealing portion of the galvannealing process. Through the use of light optical microscopy, the coating morphology development (Fe-Zn alloy layer growth) observed in cross section on both substrates was defined in three distinct stages. The three characteristic microstructures were classified as type 0 (underalloyed), type 1 (marginally alloyed), and type 2 (overalloyed) morphologies. The morphology transitions were quantitatively defined by total iron content in the coating and by the thickness of an interfacial Fe-Zn gamma phase layer. The DQSK steel coating type 1 to type 2 morphology transition occurred at an iron content of 9 to 10 wt Pct. For the titanium IF material, the same type 1 to type 2 morphology transition occurred at an iron content of 10.5 to 11.5 wt Pct and at an interfacial layer thickness of approximately 1.0 μm. An increased amount of aluminum in the galvanizing bath delayed the alloying reaction during galvannealing for both substrates. The overall inhibition effect of aluminum was less pronounced on the titanium stabilized IF material, indicating that its coating alloying kinetics were not as significantly influenced by bath aluminum content.     

Formation and capturing of nanoparticles in Cu-1 wt.%Fe alloy melt during directional solidification process

A single crystal Cu-1wt.%Fe alloy with finely dispersed iron-rich nanoparticles which keep coherent interface with the copper matrix was prepared under directional solidification.Formation of nanoparticles in the alloy melt was investigated by performing differential scanning calorimeter tests and designed water quenching experiment at a certain temperature.Results show that iron-rich nanoparticles are formed in the Cu-1wt.%Fe alloy melt before primaryα-Cu forms,which is not consistent with equilibrium phase diagram.Mechanism that iron-rich nanoparticles are uniformly captured in the matrix was described,which is that numerous nanoparticles follow Brownian motions and are engulfed in the solidified matrix which makes it possible to form uniformly distributed nanoparticles reinforced single crystal Cu-1wt.%Fe alloy.     

The distribution of chromium between ferrite and austenite and the thermodynamics of the α/γ equilibrium in the Fe-Cr and Fe-Mn Systems

New measurements of the α/γ equilibrium in the Fe-Cr system are presented and all the relevant experimental information now available, including thermodynamic data, is evaluated using a regular solution model. The two-phase field is calculated in good agreement with most of the experimental measurements. The point of minimum is obtained at 1119 K and 7.0 at. pct Cr (6.6 wt pct Cr) and the maximum solubility in austenite is 11.9 at. pct Cr (11.2 wt pct Cr). The thermodynamic quantities describing the effect of chromium on the relative stability of ferrite and austenite are similar to those for manganese. The comparison is based upon a new evaluation of the Fe-Mn system. In particular, low chromium contents are found to have a stabilizing effect on austenite up to a temperature of 1675 K.