Experimental Investigation of the Ce-Mg-Mn Isothermal Section at 723 K (450 °C) via Diffusion Couples Technique

The isothermal section of the Ce-Mg-Mn phase diagram at 723 K (450 °C) was established experimentally by means of diffusion couples and key alloys. The phase relationships in the complete composition range were determined based on six solid–solid diffusion couples and twelve annealed key alloys. No ternary compounds were found in the Ce-Mg-Mn system at 723 K (450 °C). X-ray diffraction and energy-dispersive X-ray spectroscopy spot analyses were used for phase identification. EDS line-scans, across the diffusion layers, were performed to determine the binary and ternary homogeneity ranges. Mn was observed in the diffusion couples and key alloys microstructures as either a solute element in the Ce-Mg compounds or as a pure element, because it has no tendency to form intermetallic compounds with either Ce or Mg. The fast at. interdiffusion of Ce and Mg produces several binary compounds (Ce _x Mg _y ) during the diffusion process. Thus, the diffusion layers formed in the ternary diffusion couples were similar to those in the Ce-Mg binary diffusion couples, except that the ternary diffusion couples contain layers of Ce-Mg compounds that dissolve certain amount of Mn. Also, the ternary diffusion couples showed layers containing islands of pure Mn distributed in most diffusion zones. As a result, the phase boundary lines were pointing toward Mn-rich corner, which supports the tendency of Mn to be in equilibrium with all the phases in the system.     

Solidification and Microstructural Evolution of Hypereutectic Al-15Si-4Cu-Mg Alloys with High Magnesium Contents

The low coefficient of thermal expansion and good wear resistance of hypereutectic Al-Si-Mg alloys with high Mg contents, together with the increasing demand for lightweight materials in engine applications have generated an increasing interest in these materials in the automotive industry. In the interests of pursuing the development of new wear-resistant alloys, the current study was undertaken to investigate the effects of Mg additions ranging from 6 to 15 pct on the solidification behavior of hypereutectic Al-15Si-4Cu-Mg alloy using thermodynamic calculations, thermal analysis, and extensive microstructural examination. The Mg level strongly influenced the microstructural evolution of the primary Mg₂Si phase as well as the solidification behavior. Thermodynamic predictions using ThermoCalc software reported the occurrence of six reactions, comprising the formation of primary Mg₂Si; two pre-eutectic binary reactions, forming either Mg₂Si + Si or Mg₂Si + α-Al phases; the main ternary eutectic reaction forming Mg₂Si + Si + α-Al; and two post-eutectic reactions resulting in the precipitation of the Q-Al₅Mg₈Cu₂Si₆ and θ-Al₂Cu phases, respectively. Microstructures of the four alloys studied confirmed the presence of these phases, in addition to that of the π-Al₈Mg₃FeSi₆ (π-Fe) phase. The presence of the π-Fe phase was also confirmed by thermal analysis. The morphology of the primary Mg₂Si phase changed from an octahedral to a dendrite form at 12.52 pct Mg. Any further Mg addition only coarsened the dendrites. Image analysis measurements revealed a close correlation between the measured and calculated phase fractions of the primary Mg₂Si and Si phases. ThermoCalc and Scheil calculations show good agreement with the experimental results obtained from microstructural and thermal analyses.     

Liquidus Projection of the Ag-Sn-Te Ternary System

The Ag-Sn-Te ternary system is of interest to thermoelectric applications and its liquidus projection is determined in this study. Forty Ag-Sn-Te ternary alloys are prepared and their primary solidification phases are determined. These different primary solidification phase regions include three terminal solid solutions: Ag, Sn, and Te; six binary intermediate phases: SnTe, β-Ag₅Te₃, Ag_1.9Te, Ag₂Te (assuming no phase transformation), ζ-Ag₄Sn, and ε-Ag₃Sn; and one ternary compound, AgSnTe₂. These data, together with the phase diagrams of the three constituent binary systems, are employed to construct the univariant lines of the liquidus projection. The temperature-descending directions of these univariant lines are determined using thermal analysis results and mass balance concept. The types of invariant reactions and the reaction temperatures are determined from the temperature-descending directions of the univariant lines and by thermal analysis. There are two Class I reactions, five Class II reactions, and one Class III reaction. The invariant reaction with the highest reaction temperature is L + Ag = Ag₂Te + ε-Ag₃Sn, at 992.7 ± 4 K (719.5 ± 4 °C), and that with the lowest reaction temperature is L = Sn + ε-Ag₃Sn + SnTe, at 494.2 ± 4 K (221 ± 2 °C).     

Effect of Ternary Additions on the Stability of Ordered Phases in Ni-Mo Alloys—Transmission Electron Microscopy Results and First Principles Calculations

The ordering behavior of a Ni-Mo alloy in the presence of ternary additives X (X = Al, Cr, Mn, V) has been studied using transmission electron microscopy (TEM) as well as first-principles calculations using the tight-binding–linear muffin tin orbital (TB-LMTO) method. The sequence of ordering transformations in binary Ni-Mo alloys has been shown earlier to be controlled by a competition between several fcc-based superlattices, viz. Ni₂Mo (Pt₂Mo type), Ni₃Mo (D0₂₂), Ni₄Mo (D1_a), and the so-called short-range ordered (SRO) structure characterized by the presence of {1½0} reflections. These ternary additives have been observed to stabilize the Ni₃Mo (D0₂₂) phase compared to the Ni₂Mo + Ni₄Mo phase mixture, leading to a sequence of transformation different from that obtained in binary alloys. The calculated energies of formation were observed to conform to the experimentally observed stability hierarchy in these binary intermetallics and their ternary analogues. The third element stabilizes the D0₂₂ structure by contributing to the covalent component of bonding in these compounds.     

Thermodynamic study of liquid Cu-Mg alloys by vapor pressure measurements

Thermodynamic properties of liquid Cu-Mg alloys have been determined by magnesium vapor pressure measurements over pure liquid magnesium and liquid Cu-Mg alloys, in the composition range of 11 to 90 mole pct Mg between 845 and 1345 K, employing the transpiration technique. Based on the quadratic formalism suggested by Turkdogen and Darken for binary systems, analytical expressions have been derived representing integral and partial molar thermodynamic properties as functions of composition for the two terminal regions of suN Mg = 0 to 0.33 and 0.6 to 1.0. From the measured activity values of magnesium and copper, in the liquid alloys in equilibrium with solid intermetallic compounds, standard free energies of formation of Cu₂Mg(s) and CuMg₂(s) relative to pure solid components have been calculated and expressed as functions of temperature. Extractive Metallurgy Section, Metallurgy Division     

Magnesium silicide intermetallic alloys

Methods of induction melting an ultra-low-density magnesium silicide (Mg₂Si) intermetallic and its alloys and the resulting microstructure and microhardness were studied. The highest quality ingots of Mg₂Si alloys were obtained by triple melting in a graphite crucible coated with boron nitride to eliminate reactivity, under overpressure of high-purity argon (1.3 X 10⁵ Pa), at a temperature close to but not exceeding 1105 °C ± 5 °C to avoid excessive evaporation of Mg. After establishing the proper induction-melting conditions, the Mg-Si binary alloys and several Mg₂Si alloys macroalloyed with 1 at. pct of Al, Ni, Co, Cu, Ag, Zn, Mn, Cr, and Fe were induction melted and, after solidification, investigated by optical microscopy and quantitative X-ray energy dispersive spectroscopy (EDS). Both the Mg-rich and Si-rich eutectic in the binary alloys exhibited a small but systematic increase in the Si content as the overall composition of the binary alloy moved closer toward the Mg₂Si line compound. The Vickers microhardness (VHN) of the as-solidified Mg-rich and Si-rich eutectics in the Mg-Si binary alloys decreased with increasing Mg (decreasing Si) content in the eutectic. This behavior persisted even after annealing for 75 hours at 0.89 pct of the respective eutectic temperature. The Mg-rich eutectic in the Mg₂Si + Al, Ni, Co, Cu, Ag, and Zn alloys contained sections exhibiting a different optical contrast and chemical composition than the rest of the eutectic. Some particles dispersed in the Mg₂Si matrix were found in the Mg₂Si + Cr, Mn, and Fe alloys. The EDS results are presented and discussed and compared with the VHN data. Formerly Formerly     

Response to Thermal Exposure of Ball-Milled Cu-Mg/B2O3 Powder Blends

The response to thermal exposure of ball-milled Cu-Mg/B₂O₃ powder blends was investigated in the current study to explore the potential of powder metallurgy route to produce Cu-B alloys. Cu-20Mg alloy powder was mixed with B₂O₃ and subsequently ball milled for 1 hour. Ball milling alone failed to establish a reaction between Cu-Mg compounds and B₂O₃. When the ball-milled powder blend was heated, however, B₂O₃ was reduced by CuMg₂ <773 K (500 °C). The Cu₂Mg intermetallic phase, which has survived until 773 K (500 °C), was involved in the reduction of the remaining B₂O₃ at still higher temperatures, while excess Mg reacted with B to produce MgB₂ and MgB₆ compounds. Cu-Mg alloy with predominantly the CuMg₂ phase must be utilized to take advantage of the capacity of the CuMg₂ (Cu-43 wt pct Mg) compound to reduce B₂O₃ at temperatures as low as 773 K (500 °C). Once the Cu-43Mg alloy powder is mixed with B₂O₃ and the powder blend thus obtained is ball milled and subsequently heated at 500 °C, B₂O₃ is readily reduced by CuMg₂ to yield Cu, B, and MgO. The latter can be easily removed from the powder blend by acid leaching.     

Leaching Systems of Wolframite and Scheelite: A Thermodynamic Approach

A linear correlation between free energy and enthalpy for crystalline and soluble oxocompounds based in the Sverjensky–Molling equation is used to calculate the Gibbs free energies of formation of MnWO₄ (?1172.48 ± 12.76 kJ mol^?1), H₂WO₄ (?1006.91 ± 10.36 kJ mol^?1), and Na₂WO₄ (?1455.39 ± 12.81 kJ mol^?1). Using these data with the known thermodynamic data, the equilibrium constants for reactions of leaching of scheelite and wolframite in acidic and basic media were determined. The results show that the acid route based in relatively cheap inorganic acids is desirable for scheelite digestion, despite the diffusion problems concerned with tungstic acid developed on the solid particles. Meanwhile, wolframite may be operated under favorable thermodynamics conditions by alkaline and acid processes.     

Microstructural Investigation and Phase Relationships of Fe-Al-Hf Alloys

The effect of Hf addition on microstructures, phase relationships, microhardness, and magnetic properties of Fe₅₀Al_50?n Hf _n alloys for n = 1, 3, 5, 7, and 9 at. pct has been investigated. At all investigated compositions, the ternary intermetallic HfFe₆Al₆ τ ₁ phase forms due to the limited solid solubility of Hf in FeAl phase and tends to develop a eutectic phase mixture with the Fe-Al-based phase. The Hf concentration of the eutectic composition is found to be 7 at. pct from the microstructural examinations and the eutectic phase transition temperature is determined as 1521 K (1248 °C) independent of Hf amount by differential scanning calorimetry measurements. Furthermore, the enthalpies and activation energies (based on Kissinger and Ozawa methods) of eutectic phase transitions are reported. The minimum activation energy is calculated for the fully eutectic composition. Moreover, variation of the microhardness of Fe-Al-based alloys as a function of the Hf content is investigated, and its dependence on the thermal history of the alloys is explained.     

Electron Microscopic Study on the Suction Cast In Situ Ti-Fe-Sn Ultrafine Composites

The current investigation reports detailed study on the microstructural evolution in the suction cast hypereutectic Ti₇₁Fe_29?x Sn _x alloys during Sn addition with x = 0, 2, 2.5, 3, 3.85, 4.5, 6, and 10 at. pct and the solidification of these ternary alloys using SEM and TEM. These alloys have been prepared by melting high-purity elements using vacuum arc melting furnace under high-purity argon atmosphere. This was followed by suction casting these alloys in the water-cooled split Cu molds of diameters, ? = 1 and 3 mm, under argon atmosphere. The results indicate the formation of binary eutectic between bcc solid solution ??-Ti and B2 FeTi in all alloys. ??-Ti undergoes eutectoid transformation, ??-Ti ?? ??-Ti + FeTi, during subsequent solid-state cooling, leading to formation of hcp ??-Ti and FeTi. For alloys x < 2, the primary FeTi forms from the liquid before the formation of eutectic with minute scale Ti₃Sn phase. For alloys with 2 ?? x ?? 10, the liquid is found to undergo ternary quasi-peritectic reaction with primary Ti₃Sn, L+Ti₃Sn ?? ??-Ti+FeTi, leading to formation of another kind of FeTi. In all the other alloy compositions (3.85 ?? x ?? 10), Ti₃Sn and FeTi dendrites are observed in the suction cast alloys with profuse amount of Ti₃Sn being formed for alloys with x ?? 4.5. The current study conclusively proves that the liquid undergoes ternary quasi-peritectic reaction involving four phases, L + Ti₃Sn ?? ??-Ti + FeTi, which lies at the invariant point Ti_69.2±0.8Fe_27.4±0.7Sn_3.4±0.2 (denoted by P). Below P, there is one univariant reaction, i.e., L ?? ??-Ti + FeTi for all alloy compositions, whereas above P, liquid undergoes one of the univariant reactions, i.e., L + ??-Ti ?? Ti₃Sn (Sn = 2, 2.5, 3, and 4.5 at. pct) or L + FeTi ?? Ti₃Sn for alloys (Sn = 6, 10 at. pct). For alloy with Sn = 3.85 at. pct, the ternary quasi-peritectic reaction is co-operated by two monovariant eutectic reactions, i.e., L ?? ??-Ti + FeTi below P and L ?? FeTi + Ti₃Sn above P. Detailed microstructural information allows us to construct liquidus projection of the investigated alloys. The results are critically discussed in the light of available literature data.     

Calorimetry Investigation of Phase Stability and Thermal Property in Ti-5 % Ta Alloy

An accurate measurement of enthalpy increment H _T–H _298.15 has been made for Ti-5 % Ta alloy in the temperature range of 463–1,257 K using drop calorimetry. This temperature interval covers the low temperature α + β two phase and also the α(hcp) → β(bcc) transformation domain (1,083 K ≤ T ≤ 1,183 K), in which the enthalpy versus temperature variation exhibited a clearly delineated inflection. The drop calorimetry data has been phenomenologically modelled to obtain the transformation enthalpy, Δ°H _tr ^α→β as 66 J g^?1. Further, in the α → β diffusive transformation zone the transformation kinetics has been quantitatively modelled in terms of Kolmogorov–Johnson–Mehl–Avrami model of diffusion limited phase transformation, to obtain the effective activation energy as 284 ± 10 kJ mol^?1.     

Section of the isothermal tetrahedron of the Al-Cu-Mg-Zr phase diagram at 490°C

The phase equilibria in the Al-Cu-Mg-Zr system at 490°C have been studied for Al-rich alloys with 0.3% Zr and from 0 to 10% Cu or Mg. The (Al) solid solution is found to be in equilibrium with only binary θ(CuAl₂) and ZrAl₃ and ternary S (CuMgAl₂) phases of the ternary Al-Cu-Mg system. The section of the isothermal tetrahedron of the Al-Cu-Mg-Zr phase diagram at 490°C, which corresponds to 0.3% Zr and up to 10% Cu or Mg, is constructed.     

Warm-temperature tensile ductility in Al−Mg alloys

Several binary and ternary Al alloys containing from 2.8 to 5.5 wt pct Mg were tested in tension at elevated temperatures (200°C to 500°C) over a range of strain rates (10⁻⁴ to 2.0 s⁻¹). Tensile ductilities of up to 325 pct were obtained in binary Al−Mg alloys with coarse grains deformed in the solute-drag creep regime. Under test conditions in which solute-drag creep controls deformation, Mg in concentrations from 2.8 to 5.5 wt pct neither affects tensile ductility nor influences strain-rate sensitivity or flow stress significantly. Strength is shown to increase with increasing Mg concentration, however, in the power-law-break down regime. The solute-drag creep process, which leads to superplastic-like elongations, is shown to have no observable grain-size dependence in a binary Al−Mg material. Ternary alloying additions of Mn and Zr are shown to decrease the strain-rate sensitivity during solute-drag creep, negatively influencing ductility. An important cause of reduced ductility in the ternary alloys during creep deformation is found to be a transition from necking-controlled failure in the binary alloys to cavitation-controlled failure in the ternary alloys investigated. An increase in ternary element concentration, which can increase the relative volume percentage of proeutectic products, increases cavitation.     

Thermochemical Properties of Liquid Alloys in Fe ― O and Fe ― O ― Metal Systems

An isoperibolic calorimeter has been used to determine the partial and integral enthalpies of mixing for liquid alloys in the binary Fe ― O system and ternary Fe ― O ― M ones at 1915 K. The enthalpies of mixing in these systems are high exothermic quantities, which agree with published data. It is found that the first partial enthalpy of mixing for oxygen is _280 kJ/mole. The enthalpies of mixing have been calculated from the standard enthalpies of formation Δ_f H ^º ₂₉₈ for iron oxides throughout the concentration range. The enthalpies of mixing have been calculated and measured for binary alloys in the Fe ― O system, which are correlated one with the other.     

Structure of chromium-rich Cr-Ni,Cr-Fe,Cr-Co,and Cr-Ni-Fe alloy particles made by evaporation in argon

Structural analyses were performed on alloy particles of chromium-rich Cr-Ni, Cr-Fe, Cr-Co, and Cr-Ni-Fe systems. Fine alloy particles (100 to 1000Å in diameter) were prepared by evaporation of parent alloys in argon at 20 torr. In addition, alloy structures of bulk specimens of the Cr-Ni system were investigated using X-ray diffraction techniques to confirm the results obtained from the particulate alloys. In these binary systems, δ phase with W₃O structure (A-15) and a phase withβ-uranium structure (D _b ⁸ ) were identified in addition to the α (bcc) and γ (fcc) terminal solid solutions. The compositional ranges for the σ phase in the Cr-Ni, Cr-Fe, and Cr-Co systems are from low chromium to 68, 63.4, and 62.1 wt pct Cr, respectively. The δ phase exists in the range from pure chromium to 68, 58, and 54 wt pct Cr in the respective Cr-Ni, Cr-Fe, and Cr-Co alloy systems. Similarly, in the Cr-Ni-Fe system, it was found that δ phase occurs in the chromium corner while σ phase exists in the region bridging the two binary σ phases of the Cr-Ni and Cr-Fe systems. Possible modification of phase diagrams of these systems is discussed in view of these results.     

Warm-temperature tensile ductility in Al-Mg alloys

Several binary and ternary Al alloys containing from 2.8 to 5.5 wt pct Mg were tested in tension at elevated temperatures (200 °C to 500 °C) over a range of strain rates (10⁻⁴ to 2.0 s⁻¹). Tensile ductilies of up to 325 pct were obtained in binary Al-Mg alloys with coarse grains deformed in the solute-drag creep regime. Under test conditions in which solute-drag creep controls deformation, Mg in concentrations from 2.8 to 5.5 wt pct neither affects tensile ductility nor influences strain-rate sensitivity or flow stress significantly. Strength is shown to increase with increasing Mg concentration, however, in the power-law-breakdown regime. The solute-drag creep process, which leads to superplastic-like elongations, is shown to have no observable grain-size dependence in a binary Al-Mg material. Ternary alloying additions of Mn and Zr are shown to decrease the strain-rate sensitivity during solute-drag creep, negatively influencing ductility. An important cause of reduced ductility in the ternary alloys during creep deformation is found to be a transition from necking-controlled failure in the binary alloys to cavitation-controlled failure in the ternary alloys investigated. An increase in ternary element concentration, which can increase the relative volume percentage of proeutectic products, increases cavitation.     

Phase Transformation Studies in U–xZr (x = 2, 5, 10 wt%) Alloys Using Dynamic Calorimetry

The thermo-kinetics aspects of phase transformations in U rich U–xZr binary alloys, with x = 2, 5 and 10 wt% Zr have been investigated using dynamic calorimetry. The on-heating and cooling transformations at controlled scan rates in the range, 1–99 K min^?1, have been monitored and the following transformation sequence is obtained at slow heating (3 K min^?1) of a U–2Zr alloy: (i) α or α′ (distorted orthorhombic martensite) + δ(UZr₂) → α + γ₂ (bcc phase enriched in Zr); (ii) α + γ₂ → β (tetragonal) + γ₂; (iii) β + γ₂ → β + γ₁ (bcc phase enriched in U); (iv) β + γ₁ → γ; (v) γ (bcc) → liquid (melting). Similar transformation sequence for other compositions with varying enthalpy effects has been witnessed for 5 and 10 Zr alloys. The observed transformation characteristics are rationalized for the effect of Zr content and heating/cooling rate variations.     

Microstructure and High Temperature Impression Creep Properties of Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) Alloys

The current study has investigated the influence of zirconium (Zr) addition to Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) alloys prepared using argon arc melting on the microstructure and impression properties at 448–498 K under constant stress of 380 MPa. Microstructural analysis of as-cast Mg–3Ca–xZr alloys showed grain refinement with Zr addition. The observed grain refinement was attributed to the growth restriction effect of Zr in hypoperitectic Mg–3Ca–0.3 wt% Zr alloys. Heterogeneous nucleation of α-Mg in properitectic Zr during solidification resulted in grain refinement of hyperperitectic Mg–3Ca–0.6 wt% Zr and Mg–3Ca–0.9 wt% Zr alloys. The hardness of Mg–3Ca–xZr alloys increased as the amount of Zr increased due to grain refinement and solid solution strengthening of α-Mg by Zr. Creep resistance of Mg–3Ca–xZr alloys increased with the addition of Zr due to solid solution strengthening of α-Mg by Zr. The calculated activation energy (Q_a) for Mg–3Ca samples (131.49 kJ/mol) was the highest among all alloy compositions. The Q_a values for 0.3, 0.6 and 0.9 wt% Zr containing Mg–3Ca alloys were 107.22, 118.18 and 115.24 kJ/mol, respectively.