Phase equilibria of the ternary Al-Cu-Ni system and interfacial reactions of related systems at 800 °C

A series of Al-Cu-Ni alloys of various compositions were made and annealed at 800 °C. The equilibrium phases were studied by metallography, X-ray diffraction (XRD) analysis, and electron probe microanalysis. The isothermal section of the ternary Al-Cu-Ni system at 800 °C was then determined based on these experimental results and the available phase relationship knowledge of the three constituent binary systems. No ternary compound was found. All three phases, AlNi₃, AlNi, and Al₃Ni₂, have very high ternary solubility, especially the AlNi phase, which almost reaches the binary Al-Cu side. However, no continuous solid solution was formed between the AlNi phase and any of the binary Al-Cu phases. Interfacial reactions of Al/Ni, Al/Cu, Al-Cu/Ni, and Al-Ni/Cu at 800 °C were investigated by using reaction couple techniques. The results showed that Al₃Ni and Al₃Ni₂ phases were formed in the Al/Ni couples; β-AlCu₄, γ ₁-Al₄Cu₉, and ɛ ₂-Al₂Cu₃ phases were formed in the Al/Cu couples. As for the results in the Al-2 at. pct Ni/Cu, Al-5 at. pct Ni/Cu, and Al-2 at. pct Cu/Ni, Al-4.5 at. pct Cu/Ni, and Al-6 at. pct Cu/Ni were similar to those in the binary Al/Cu and Al/Ni couples, respectively. A different reaction path was found in the Al-7.5 at. pct Cu/Ni couples, and an AlNi solid solution layer was formed instead of the Al₃Ni and Al₃Ni₂ phases.     

Microstructure and phase relations for Ti-Mo-Al alloys

The influence of aluminum additions to a Ti-7 at. pet Mo alloy on the phase equilibria was investigated. The microstructures of the alloys, Ti-7 pct Mo-7 pct Al and Ti-7 pct Mo-16 pct Al, were determined by light and electron microscopy. It was found that with increasing aluminum concentration the formation of the metastable w phase was suppressed. In the Ti-7 pct Mo-16 pct Al alloy the β phase decomposed upon quenching by precipitating coherent, ordered particles having a B2 type of crystal structure (β₂). At low temperatures the equilibrium phases for this alloy were β + α+ β ₂, whereas at high temperature (850° to 950°C) the Ti₃Al phase was in two-phase equilibrium with the β phase. The four-phase equilibrium which exists at a temperature of about 550°C involves the reaction β + Ti₃Al ⇌ α + β₂. G. LUETJERING, formerly Staff Member Materials Research Center, Allied Chemical Corp., Morristown, N. J.,     

The vanadium-platinum constitution diagram

The system V-Pt was investigated over the entire composition range by metallography, X-ray diffraction and electron microprobe studies. There are at least four equilibrium intermediate phases in this system and they are stable to progressively higher temperatures with increasing vanadium concentration. The phases which have been observed are: γ^′, cubic, Cu₃Au type; θ, tetragonal, TiAl₃ type; δ, orthorhombic, MoPt₂ type; ζ, orthorhombic, AuCd type; and β, cubic, Cr₃Si type (A15). The gg^′ phase is possibly metastable. A very stable ribbon-like growth of ζ phase in the fcc platinum terminal solid solution has been observed in alloys containing about 43 at. pct V. The platinum terminal solid solution forms a congruent melting maximum at about 1805°C. A eutectic reaction occurs at 1720° ± 10°C and a peritectic reaction is indicated at 1800° ± 10°C. Vanadium is soluble in the fcc platinum terminal solid solution up to about 57 at. pct at 1720°C. Platinum dissolves only to the extent of about 12 at. pct at 1800°C in bcc α-V.     

Kinetics and phase transformation evaluation of Fe-Zn-Al mechanically alloyed phases

Fixed composition ratios of Fe and Zn corresponding to γ-(Fe₃Zn₁₁₀), Γ₁-(Fe₅Zn₂₁), δ-(FeZn₇), and ζ-(FeZn₁₃) with the addition of 5 pct Al (wt) were ball milled in an argon gas atmosphere to form homogenous alloys. Nonisothermal kinetic analyses of the mechanically alloyed materials, based on differential scanning calorimetry (DSC) measurements, revealed two diffusion-controlled processes during the evolution of the δ+5 pct Al and ζ+5 pct Al compositions with activation energies of 227±2 and 159±1 kJ/mole, respectively. Other endothermic and exothermic reactions detected for these compositions are consistent with the Fe-Zn-Al equilibrium phase systems with respect to the formation of the Fe₃Al, Fe₂Al₅, and δ-FeZn₇ phases Based on the evidence of FeAl₂ formation at 440 °C for the ζ+5 pct Al composition from X-ray diffraction (XRD) and DSC measurements, the revision/re-evaluation of the Fe-Zn-Al equilibrium phase diagrams is proposed. The Γ+5 pct Al and Γ₁+5 pct Al compositions evolved similarly through the same fields, except at 400 °C, where the former consisted of α-Fe + Γ + δ, while the later was without the Γ phase.     

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.     

Iron intermetallic phases in the Al corner of the Al-Si-Fe system

The iron intermetallics observed in six dilute Al-Si-Fe alloys were studied using thermal analysis, optical microscopy, and image, scanning electron microscopy/energy dispersive X-ray, and electron probe microanalysis/wavelength dispersive spectroscopy (EPMA/WDS) analyses. The alloys were solidified in two different molds, a preheated graphite mold (600 °C) and a cylindrical metallic mold (at room temperature), to obtain slow (∼0.2 °C/s) and rapid (∼15 °C/s) cooling rates. The results show that the volume fraction of iron intermetallics obtained increases with the increase in the amount of Fe and Si added, as well as with the decrease in cooling rate. The low cooling rate produces larger-sized intermetallics, whereas the high cooling rate results in a higher density of intermetallics. Iron addition alone is more effective than either Si or Fe+Si additions in producing intermetallics. The alloy composition and cooling rate control the stability of the intermetallic phases: binary Al-Fe phases predominate at low cooling rates and a high Fe:Si ratio; the β-Al₅FeSi phase is dominant at a high Si content and low cooling rate; the α-iron intermetallics (e.g., α-Al₈Fe₂Si) exist between these two; while Si-rich ternary phases such as the δ-iron Al₄FeSi₂ intermetallic are stabilized at high cooling rates and Si contents of 0.9 wt pct and higher. Calculations of the solidification paths representing segregations of Fe and Si to the liquid using the Scheil equation did not conform to the actual solidification paths, due to the fact that solid diffusion is not taken into account in the equation. The theoretical models of Brody and Flemings^[44] and Clyne and Kurz^[45] also fail to explain the observed departure from the Scheil behavior, because these models give less weight to the effect of solid back-diffusion. An adjusted 500 °C metastable isothermal section of the Al-Si-Fe phase diagram has been proposed (in place of the equilibrium one), which correctly predicts the intermetallic phases that occur in this part of the system at low cooling rates (∼0.2 °C/s).     

Iron intermetallic phases in the Al corner of the Al-Si-Fe system

The iron intermetallics observed in six dilute Al-Si-Fe alloys were studied using thermal analysis, optical microscopy, and image, scanning electron microscopy/energy dispersive X-ray, and electron probe microanalysis/wavelength dispersive spectroscopy (EPMA/WDS) analyses. The alloys were solidified in two different molds, a preheated graphite mold (600°C) and a cylindrical metallic mold (at room temperature), to obtain slow (}0.2 °C/s) and rapid (}15 °C/s) cooling rates. The results show that the volume fraction of iron intermetallics obtained increases with the increase in the amount of Fe and Si added, as well as with the decrease in cooling rate. The low cooling rate produces larger-sized intermetallics, whereas the high cooling rate results in a higher density of intermetallics. Iron addition alone is more effective than either Si or Fe+Si additions in producing intermetallics. The alloy composition and cooling rate control the stability of the intermetallic phases: binary Al-Fe phases predominate at low cooling rates and a high Fe:Si ratio; the β-Al₅FeSi phase is dominant at a high Si content and low cooling rate; the α-iron intermetallics (e.g., α-Al₈Fe₂Si) exist between these two; while Si-rich ternary phases such as the δ-iron Al₄FeSi₂ intermetallic are stabilized at high cooling rates and Si contents of 0.9 wt pct and higher. Calculations of the solidification paths representing segregations of Fe and Si to the liquid using the Scheil equation did not conform to the actual solidification paths, due to the fact that solid diffusion is not taken into account in the equation. The theoretical models of Brody and Flemings^[44] and Clyne and Kurz^[45] also fail to explain the observed departure from the Scheil behavior, because these models give less weight to the effect of solid back-diffusion. An adjusted 500°C metastable isothermal section of the Al-Si-Fe phase diagram has been proposed (in place of the equilibrium one), which correctly predicts the intermetallic phases that occur in this part of the system at low cooling rates (}0.2 °C/s).     

Precipitation in a Cu-30 Pct Ni-1 Pct Nb alloy

Decomposition of a Cu-30 pct Ni-1 pct Nb alloy on aging in the range of 866 K (600°C) to 1073 K (800°C) was investigated. The initial decomposition, concomitant with age hardening, occurred through the precipitation of body centered tetragonal metastable Ni₃Nb-γ” precipitates on the 100 matrix planes. Equilibrium orthorhombicβ phase formed either through a grain boundary cellular reaction at low temperature (≤973 K (700°C)) or as Widmanstaettenplatelets on the 1ll planes at higher temperatures (≥1073 K (800°C)) with the following crystallographic relationship: (0l0)_β//111_γ [100]β//[1•11]_γ. Based on the observations, a schematic transformation sequence is presented.     

The compctition between martensite and omega in quenched Ti-Nb alloys

A careful experimental study of the phase transformations which occur in annealed β phase Ti-Nb alloys during quenching has been completed. The compctition of the α″ and ω phases to form in alloys of 20 to 70 at. pct Nb was investigated as a function of quench rate and alloy composition. Particular attention was paid to the interstitial content and chemical homogeneity of the alloys. The martensitic α″ phase was found only in 20 and 25 at. pct Nb alloys, and then only using fast water quenches of ~300 °C/sec. Under slower quench conditions,e.g., ~0.3 to 3 °C/sec, ω phase precipitates were found in these alloys and in 30 and 35 at. pct Nb alloys. Evidence of “diffuse” ω phase precipitation was observed in alloys up to 50 at. pct Nb. Only alloys of 60 and 70 at. pct Nb were found to retain the single phaseβ structure upon quenching. These results constitute the first part of a study of the stable and metastable equilibria of the Ti-Nb alloy system. Formerly a Graduate Student in the Materials Science Program at the University of Wisconsin-Madison.     

Characterization of hot deformation behavior of brasses using processing maps: Part II. β Brass and α-β brass

The hot deformation behaviors of β brass in the temperature range of 550°C to 800°C and α-β brass in the temperature range of 450°C to 800°C have been characterized in the strain rate range of 0.001 to 100 s⁻¹ using processing maps developed on the basis of the Dynamic Materials Model. The map for β brass revealed a domain of superplasticity in the entire temperature range and at strain rates lower than 1 s⁻¹, with a maximum efficiency of power dissipation of about 68 pct. The temperature variation of the efficiency of power dissipation in the domain is similar to that of the diffusion coefficient for zinc in β brass, confirming that the diffusion-accommodated flow controls the superplasticity. The material undergoes microstructural instability in the form of adiabatic shear bands and strain markings at temperatures lower than 700°C and at strain rates higher than 10 s⁻¹. The map for α-β brass revealed a wide domain for processing in the temperature range of 550°C to 800°C and at strain rates lower than 1 s⁻¹, with a maximum efficiency of 54 pct occurring at about 750°C and 0.001 s⁻¹. In the domain, the α phase undergoes dynamic recrystallization and controls the hot deformation of the alloy, while the β phase deforms superplastically. At strain rates greater than 1 s⁻¹, α-β brass exhibits microstructural instabilities manifested as flow rotations at lower temperatures and localized shear bands at higher temperatures.     

A pressure-composition-temperature study of Zr-Nb-H system

The solubility of hydrogen was determined in the (Zr + 5 wt pct Nb)-H₂, (Zr + 10 wt pct Nb)-H₂, and (Zr + 20 wt pct Nb)-H₂ systems as a function of composition, temperature (700° to 950°C) and hydrogen equilibrium pressure (0.5 to 760 mm Hg). The position of boundariesβ - (β + δ) and(β + δ)-δ were determined in each of the above three systems. Niobium significantly reduces the solubility of hydrogen in theβ andδ phases and increases the equilibrium hydrogen pressure for any fixed concentration. The equilibrium pressure-temperature relations in the two phase region (β + δ) were derived and the heat of formation ofδ-hydride from saturatedβ-Zr, ΔH _β → δ, were determined. The value of ΔH _β → δ increases up to about 5 wt pct Nb after which the effect of niobium seems to be insignificant. The maximum hydrogen pick-up of zirconium at room temperature decreases with increasing niobium content of the alloy.     

The niobium (columbium)-palladium constitution diagram

The Nb-Pd system was investigated over the entire composition range by metallography and X-ray diffraction analysis. The solubility limits of terminal and intermediate phases and solidus temperatures were determined. α-Nb dissolves ∼36 at. pct Pd at. 1520°C and ∼20 at. pct Pd at 800°C; α-Pd dissolves ∼31 at. pct Nb at 1610°C and ∼18 at. pct Nb at temperatures below 1500°C. The presence of three intermediate phases NbPd₂ (MoPt₂-type), α-NbPd₃ (TiAl₃-type), and β-NbPd₃ (β-NbPd₃-type) was confirmed; NbPd₂ melts at 1610°C and one of the NbPd₃ phases transforms at the same temperature into α-Pd solid solution which melts at 1625°C. In addition, an approximately equiatomic high-temperature phase α-NbPd with a homogeneity range of ∼11 at. pct was found which melts at 1520 to 1565°C and probably is an extension of and isomorphous with the α-Pd solid solution. Five three-phase reactions are described, and crystal chemical relationships are discussed. D. P. PARKER formerly with MIT . R. C. MANUSZEWSKI formerly with the ADAHF Research Unit at NBS.     

Phase relationships in the neodymium-magnesium alloy system

The Nd-Mg system was studied using differential thermal analysis (DTA), X-ray examination, metallography, and microprobe analysis. The following intermetallic compounds were found to exist and their crystal structures confirmed or determined: NdMg (cubic, cP2 CsCl type, melting point 800 °C), NdMg₂ (cubic, cF24 MgCu₂ type, peritectic formation ∼755 °C), NdMg₃ (cubic, cF16 BiF₃ type, melting point 780 °C), and Nd₅Mg₄₁ (tetragonal, tI92 Ce₅Mg₄₁ type, decomposes peritectically at 560 °C). The NdMg₂ phase undergoes a eutectoidal decomposition at 660 °C. Three eutectic equilibria were observed to occur at 42.5 at. pct Mg and 775 °C, 64.5 at. pct Mg and 750 °C, and 92.5 at. pct Mg and 545 °C, respectively. In the Nd-rich alloys, previously determined data^[15] concerning the Mg solubility in α-Nd (8.2 at. pct Mg, ≈550 °C) were accepted. The Mg solubility in β-Nd was evaluated as 34 at. pct Mg at 775 °C. The β-Nd phase was observed to decompose eutectoidally at 17 at. pct Mg and 545 °C. Moreover, in the Mgrich alloys, a metastable NdMg₁₂ phase (tetragonal, tI26 ThMn₁₂ type) was observed in samples quenched from the liquid. The general properties of the Nd-Mg phases are compared with those of the R-Mg compounds and briefly discussed.     

A sintering study on the β-spodumene-based glass ceramics prepared from gel-derived precursor powders with LiF additive

Beta-spodumene (Li₂O·Al₂O₃·4SiO₂, LAS) powders were prepared by a sol-gel process using Si(OC₂H₅)₄, Al(OC₄H₉)₃, and LiNO₃ as precursors and LiF as a sintering aid agent. Dilatometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and electron diffraction (ED) were utilized to study the sintering, phase transformation, microstructure, and properties of the β-spodumene glass-ceramics prepared from the gel-derived precursor powders with and without LiF additives. For the LAS precursor powders containing no LiF, the only crystalline phase obtained was β-spodumene. For the pellets containing less than 4 wt pct LiF and sintered at 1050 °C for 5 hours the crystalline phases were β-spodumene and β-eucryptite (Li₂O·Al₂O₃·2SiO₂). When the LiF content was 5 wt pct and the sintering process was carried out at 1050 °C for 5 hours, the crystalline phases were β-spodumene, β-eucryptite (triclinic), and eucryptite (rhombohedral (hex.)) phases. With the LiF additive increased from 0.5 to 4 wt pct and sintering at 1050 °C for 5 hours, the open porosity of the sintered bodies decrease from 30 to 2.1 pct. The grains size is about to 4 to 5 μm when pellect LAS compact contains LiF 3 wt pct as sintered at 1050 °C for 5 hours. The grains size grew to 8 to 25 μm with a remarkable discontinuous grain growth for pellet LAS compact contain LiF 5 wt pct sintered at 1050 °C for 5 hours. Relative densities greater than 90 pct could be obtained for the LAS precursor powders with LiF > 2 wt pct when sintered at 1050 °C for 5 hours. The coefficient of thermal expansion of the sintered bodies decreased from 8.3 × 10⁻⁷ to 5.2 × 10⁻⁷/°C (25 °C to 900 °C) as the LiF addition increased from 0 to 5 wt pct.     

The Fe−Ho binary system

The Fe?Ho phase diagram was determined on the basis of data obtained by X-ray diffraction, metallographic and differential thermal analysis techniques. Since emphasis was centered in the region where intermetallic compounds predominate, neither the iron nor holmium terminal regions were included in this study. Eutectic reactions were found to occur at 16.5 wt pct Fe and 875° C, 61 wt pct Fe and 1284° C, and 79 wt pct Fe and 1338° C. The congruent melting points of the compounds Ho₆Fe₂₃ and Ho₂Fe₁₇ were found to be 1332° and 1343° C, respectively. Two other intermetallic compounds were found, HoFe₂ and HoFe₃, and had peritectic decomposition temperatures of 1288° and 1293° C, respectively.     

Isothermal section of the ternary Sn-Cu-Ni system and interfacial reactions in the Sn-Cu/Ni couples at 800 °C

The isothermal section of the Sn-Cu-Ni system at 800 °C has been experimentally determined. There is no ternary compound. A solid solution with a very wide compositional range, the γ phase is formed between the Ni₃Sn(H) phase and Cu₄Sn(H) phase; however, both of these two binary phases are not stable at 800 °C. The binary Ni₃Sn₂ phase also has extensive ternary solubility. The homogeneity ranges of both the γ and Ni₃Sn₂ phases are very large in parallel to the Cu-Ni side, but relatively narrow along the Sn direction. This phenomenon indicates that Cu and Ni are exchangeable in both phases. Three kinds of reaction couples, Sn-55 at. pct Cu/Ni, Sn-65 at. pct Cu/Ni, and Sn-75 at. pct Cu/Ni, were prepared and reacted at 800 °C for 5 to 20 minutes. The reaction paths are liquid/Ni₃Sn₂/γ/Ni₃Sn(L)/Ni for the Sn-55 at. pct Cu/Ni and Sn-65 at. pct Cu/Ni couples, and the reaction path is liquid/γ/Ni₃Sn(L)/Ni for the Sn-75 at. pct Ni couples.     

An experimental study and thermodynamic evaluation of the Fe-Mo-Ti system at 1000 °C

The phase equilibria in the Fe-Mo-Ti system at 1000 °C have been studied using the diffusion couple technique. The various phases formed during annealing at 1000 °C for 480 hours were examined by X-ray diffraction, and no new ternary phase was observed. The equilibrium com-positions of these phases and some tie-lines were measured by means of electron probe micro-analysis. The results show that the solubility of Mo in the á phase Fe₂Ti ranges from 0 to 25.03 at. pct following the formula Fe₂(Mo,Ti) and solubility of Ti in the μ phase ranges from 0 to 14.55 at. pct following Fe₇(Mo,Ti)₆, whereas the solubility of Mo in the FeTi phase is negligible. It is expected that Fe₂Mo and Fe₂Ti can form a complete series of solid solutions below 900 °C. On the basis of the sublattice models, the thermodynamic properties of the Fe-Mo-Ti system at 1000 °C have been evaluated from the present results. An isothermal section calculated at 1000 °C is presented, and it shows good agreement with the experiments. Formerly Graduate Student, Department of Physical Metallurgy and Ceramics, Royal Institute of Technology, 10044, Stockholm, Sweden.     

The titanium-rich end of the Ti-Cd phase diagram

Ti-Cd alloys containing up to 30 at. pct Cd have been prepared by diffusing cadmium from the vapor phase into pure titanium. Phase relations in these alloys have been explored by metallographic and X-ray techniques. Cadmium has quite a large solubility in theβ phase of titanium at 1000°C. Addition of cadmium decreases theα-β transformation temperature, forming a eutectoid at approximately 785°C. The solubility of cadmium inα titanium at the eutectoid temperature is approximately 6.5 at. pct, decreasing with decreasing temperature. The phase in equilibrium with saturatedα titanium is an intermetallic compound based on the composition Ti₂Cd.     

Transient oxidation of Single-Crystal β-NiAl

The transient oxidation of β-NiAl in air at 800 °C and 1100 °C has been studied using electron microscopy. The oxide scale consists predominatly of metastable Al₂O₃ phases. θ-Al₂O₃ is the major oxide phase within 10.0 hr of oxidation at 800 °C and 0.1 hr at 1100 °C. The scales form epitaxially on (001)_β and (012)_β specimens throughout the transient stage, whereas the degree of preferred oxide orientation decreases with oxidation time on (011)_β and (111)_β specimens. The orientation relationships reflect the small mismatch between parallel close-packed directions in the metal and in the cation sublattice of the oxides. The correlation of distinctive oxide surface morphologies with internal structural defects indicates the strong tendency of the Al₂O₃ scale to growvia short-circuit diffusion paths.