Grain refinement in aluminum alloyed with titanium and boron

The aluminum corner of the ternary Al-B-Ti diagram was explored. A eutectic: Liq — Al + TiAl₃ + (Al, Ti)B₂ was found at approximately 0.05 wt pct Ti, 0.01 wt pct B; 659.5‡C. TiB₂ and A1B₂ form a continuous series of solid solutions, but no distinct ternary phase was found. The addition of boron to aluminum-titanium alloys expands the field of primary crystallization of TiAl₃ toward lower titanium contents and steepens the liquidus. In equilibrium conditions, pronounced grain refinement is found only in alloys in which TiAl₃ is primary and nucleates the aluminum solid solution before any other impurity can act. The peritectic reaction facilitates this priority but it is not necessary for grain refinement. Because of the low diffusivity of titanium and boron in aluminum, equilibrium is seldom attained and in commercial practice grain refinement by TiAl₃ is found also outside its equilibrium field of primary crystallization.     

Constitution of the Lead-Tin-Strontium System up to 36 Atomic Percent Sr

The constitution of the Pb-Sn-Sr system from the Pb-Sn binary up to 36 at. pct Sr was determined by differential thermal analysis, metallography, microprobe analysis, and X-ray diffraction. Pb₃Sr forms a continuous series of solid solutions with Sn₃Sr, and is referred to here as the8 phase. Sn₄Sr was the only other intermetallic phase found and is designated here as γ. A eutectic-like trough is formed between (Pb) and δ. It originates at 1.0 at. pct Sr and 324.5 °C (the (Pb)/Pb₃Sr eutectic) and falls monotonically to ~75 at. pct Pb, 24.5 at. pct Sn, and 0.45 at. pct Sr at 283 °C. At 283 °C, a Class II, four-phase reaction occurs: L + δ→ (Pb) + γ. A eutectic-like trough between (Pb) and γ falls from the four-phase plane at 283 °C to the ternary eutectic at ~26 at. pct Pb, ~74 at. pct Sn and <0.3 at. pct Sr at 182 °C. The ternary eutectic reaction is L → (Pb) + (Sn) + γ.     

Composites ofγ + TaC in the Ni−Ta−C ternary system

The Ni−Ta−C ternary system has been studied at the Ni-rich end of the phase diagram. The investigation was directed toward developing a detailed picture of γ+TaC composites. Alloys were melted with Ta/C atomic ratios of 0.79 to 3.33 in an attempt to define the composition range that would produce two-phase γ+TaC eutectics. The liquidus trough rises in temperature across the ternary diagram moving away from the Ni−C eutectic (1320°C) and toward the Ni−Ni₃Ta eutectic (1380°C). Bulk chemistries were determined for aligned regions to map the liquidus trough compositions. Ratios of Ta/C atoms varied from 1.3 to 8.8 in the aligned regions. Matrix composition was determined by electron microprobe analysis, and lattice parameters of extracted TaC fibers were measured by X-ray diffraction. Fiber compositions ranged from TaC_0.99 to TaC_0.97 as the Ta/C ratio of the aligned region increased. The matrix compositions and TaC stoichiometries were used to map tie-lines across the ternary diagram. Volume fraction and microstructural features of the TaC phase were also studied. The volume fraction of TaC decreased from 6.7 vol pct to 1.7 vol pct as Ta/C increased from 1.3 to 8.8. The decreasing volume fraction can be explained by a lever-arm rule application for the ternary phase diagram, based on the liquidus trough and tie-line compositions determined in this study. The TaC growth axis was <111> in each case, but the carbide morphology changed progressively across the phase diagram. The change in morphology is primarily a consequence of the change in volume fraction. Implications of the findings of this study for more complex γ+MC eutectics will be discussed.     

The high temperature phase diagrams for zirconium-molybdenum and hafnium-molybdenum

The high temperature regions of the Zr−Mo and Hf−Mo binary phase diagrams have been constructured from temperature-composition data obtained by gravimetric and pyrometric methods. The liquidus curves were obtained directly from the measurements of saturation solubilities of molybdenum (single crystal) in liquid Zr and Hf. The solubility results are supported by electron microprobe analyses which identify the formation of thin (∼10 μm) layers of nearly stoichiometric compounds ZrMo₂ and HfMo₂ on the surface of the single crystal molybdenum below the respective peritectic temperatures 1918±5 and 2206±5°C. These thin layers and the negligible diffusion zones of Zr and Hf in single crystal molybdenum do not significantly affect the measured solubilities. The diffusion coefficient of Hf in Mo-single crystal at 2080°C is ∼5×10⁻¹² m² s⁻¹. The melting, solidus, liquidus, eutectic and peritectic temperatures were directly measured by pyrometrically observing the partial or complete destruction of “black-body” conditions inside an effusion cell with the appearance of a liquid phase that forms a highly reflecting mirror. The melting points of Zr and Hf metals, 1860±3 and 2228±3°C, respectively, are in good agreement with previously assessed values. The respective eutectic temperatures peratures and compositions 1551±2°C, 29.0±0.5 at. pct Mo and 1896±3°C, 40.5 at. pct Mo, are considerably more precise and only in fair agreement with previously measured or estimated values. The liquidus composition at the peritectic temperature for the Zr−Mo binary is precisely fixed at 54.0±1.0 at. pct Mo and that for the Hf−Mo binary is 61 ±3 at. pct Mo. The thermodynamic activities of molybdenum in the liquid Zr−Mo alloy indicate positive deviations from Raoult's Law. temporarily attached to the Chemistry Division, Argonne National Laboratory, Argonne IL 60439 This work was performed at Argonne National Laboratory under the auspices of the U.S. Energy Research and Development Administration     

The Fe-rich corner of the metastable C-Cr-Fe liquidus surface

The liquidus surface of the C-Cr-Fe system has been experimentally determined in the Fe-rich region —C ≤6 wt pct, Cr ≤40 wt pct —using a sensitive differential thermal analysis technique, along with optical and scanning electron microscopy and X-ray diffraction. Previous liquidus surfaces for this system have differed on the extent of the (Cr,Fe)₂₃C₆ liquidus field, with one version reporting its existence at ∼20 wt pet Cr, and others finding that it did not occur at Cr levels of less than ∼60 wt pct. The present investigation provides evidence in favor of the second contention, with the (Cr,Fe)₂₃C₆ field not being detected at Cr ≤40 wt pct. Changes are proposed to the accepted liquidus surface in respect of the compositions of the invariant reactions—L + αδFe ⇌γFe + (Cr,Fe)₇C₃ andL + (Cr,Fe)₇C₃ ⇌γFe + (Fe,Cr)₃C —and of the monovariant eutectic valley—L⇌ γFe + (Cr,Fe)₇C₃.     

Phase diagram of the Al2O3-ZrO2-Sm2O3 system. III. Solidus surface and phase equilibria in alloy crystallization

A projection has been constructed for the solidus surface in the Al₂O₃-ZrO₂-Sm₂O₃ phase diagram on the plane of the concentration triangle, which consists of seven isothermal three-phase fields corresponding to two nonvariant equilibria of eutectic type and five nonvariant equilibria of peritectic type, and also eight lineated surfaces for the end of crystallization of the binary eutectics. The highest temperature on the solidus surface is 2710°C, the melting point of pure ZrO₂, while the lowest is 1680°C, the temperature of the triple eutectic Al + F + SA. No ternary phases or appreciable regions of solid solutions based on the components and the binary compounds are observed. Data on the bounding binary systems, the liquidus and solidus surfaces have been used to construct the phase-equilibrium (melting) diagram together with a reaction scheme for the equilibrium crystallization of alloys in the Al₂O₃-ZrO₂-Sm₂O₃ system. __________ Translated from Poroshkovaya Metallurgiya, Nos. 5–6(449), pp. 56–64, May–June, 2006.     

Mg-Pb phase diagram and phase transformations in the intermetallic compounds Mg2Pb and β

The liquidus curve for the Mg-Pb system was redetermined, and its slope was used to assess phase transformations in theβ' + Pb-rich liquid phase field. A peritectic reaction occurred at 538.7 °C when Mg₂Pb decomposed into a Mg-rich liquid andβ' (a Mg-Pb compound containing 35.15 at. pct Pb, or 0.3515 N_Pb, the atomic fraction of Pb) which melted congruently at 548.5 °C, confirming the work of Eldridgeet al. ^[1] Whenβ' was cooled, a series of reactions occurred with the progressive rejection of Pb, this catatectic reaction terminated at 249 °C, 4 °C below the temperature of the Pb-rich eutectic at 83.88 at. pct Pb and 252.6 °C. This finding is contrary to that of Eldridgeet al.,w as they reported the catatectic reaction terminated at 291 ± 5 °C. The rejection of Pb from an ingot ofβ' was recorded as a time-lapse series of photographs. The phase transformations resulting from the catatectic reaction and several polymorphic transformations of the intermediate products have been identified in the temperature range 548.5 °C to 249 °C. The identification of the reactions at 252.6 °C and 249 °C has clarified this region of the phase diagram, as both of these values have been reported as the eutectic temperature. Finally, two polymorphic transformations of Mg₂Pb at 229 °C and 208 °C were identified and provided a basis for the identification of the final stage of the catatectic reaction at 249 °C.     

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.,     

Phase equilibria in the binary rare-earth alloys: The erbium-magnesium system

The Er-Mg system was examined using differential thermal analysis (DTA), X-ray examination, metallography, and microprobe analysis. Four intermediate phases are found to exist, and their crystal structures have been confirmed or determined as the following:β phase (≈Er₂Mg) (cubic, cI2-W type, peritectic formation 1255 °C); ErMg (cubic, cP2-CsCl type, peritectic formation 830 °C); ErMg₂ (hexagonal, hP12-MgZn₂ type, peritectic formation 670 °C); and Er₅Mg₂₄ (cubic, cI58-α-Mn type, peritectic formation 600 °C). Theβ phase undergoes a eutectoidal decomposition at 680 °C and 30.5 at. pct Mg. A eutectic reaction was observed to occur at 570 °C and 89.5 at. pct Mg. Comparisons of the general properties between the ErMg phases and with those of the other R-Mg compounds (R = rare earth) are briefly discussed. Properties and structures of the R-Mg, R-rich alloys are specially considered and compared with those of a few groups of rare-earth alloys. The alloying behavior of R-rich R-Me alloys (R = Ho, Er, Tm, Lu; Me = Mg, Cd, In, Tl) is systematically presented and/or predicted.     

Equilibrium studies on a chi phase-strengthened ferritic alloy

The phase relationships for a quaternary ferritic alloy with promising high temperature properties were investigated. The alloy of interest has the composition Fe-13 pct Cr-1.5 pct Mo-3.5 pct Ti and owes its high temperature strength to the presence of a Chi phase precipitate. A “quasi binary” section representing the phase equilibria up to 1250°C is proposed on the basis of evidence from microprobe, thermal analysis, metal-lographic and X-Ray examinations. There is a marked temperature dependence in the solid solubility of the Chi phase in the ferrite matrix which becomes particularly pro-nounced above 1000°C. An eutectic horizontal has been identified at 1325°C. The Chi phase exhibits a wide range of stoichiometry, extending from the ternary Chi phase, Fe₃₆Cri₁₂Mo₁₀ to Fe₃₆Cr₁₂Mo₃Ti₇ accompa-nied by a regular increase in lattice par-ameter and a decrease in the solidus temperature from 1455 to 1350°C.     

Determination of Solid Fraction from Cooling Curve

A new method to determine directly the solid fraction using the cooling curve was proposed for solidification of undercooled melts. Then, to construct three different baselines, a sudden function ξ _α (x) is introduced. In terms of the ξ _α (x) function, accordingly, the solid fractions during solidification of Ni-3.3 wt pct B, Al-7 wt pct Si, Al-14 wt pct Cu, and Fe-4.56 wt pct Ni alloys were predicted. The predictions of the primary, the regular lamellar eutectic, the anomalous eutectic, and the peritectic phases from cooling curves of the solidified samples coincide with the results of measurement or the available methods.     

The neodymium-gold phase diagram

The Nd-Au phase diagram was studied in the 0 to 100 at. pct Au composition range by differential thermal analysis (DTA), X-ray diffraction (XRD), optical microscopy (LOM), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). Six intermetallic phases were identified, the crystallographic structures were determined or confirmed, and the melting behavior was determined, as follows: Nd₂Au, orthorhombic oP12-Co₂Si type, peritectic decomposition at 810 °C; NdAu, R.T. form, orthorhombic oP8-FeB type, H.T. forms, orthorhombic oC8-CrB type and, at a higher temperature, cubic cP2-CsCl type, melting point 1470 °C; Nd₃Au₄, trigonal hR42-Pu₃Pd₄ type, peritectic decomposition at 1250 °C; Nd₁₇Au₃₆, tetragonal tP106-Nd₁₇Au₃₆ type, melting point 1170 °C; Nd₁₄Au₅₁, hexagonal hP65-Gd₁₄Ag₅₁ type, melting point 1210 °C; and NdAu₆, monoclinic mC28-PrAu₆ type, peritectic decomposition at 875 °C. Four eutectic reactions were found, respectively, at 19.0 at. pct Au and 655 °C, at 63.0 at. pct Au and 1080 °C, at 72.0 at. pct Au and 1050 °C, and, finally, at 91.0 at. pct Au and 795 °C. A catatectic decomposition of the (βNd) phase, at 825 °C and ≈1 at. pct Au, was also found. The results are briefly discussed and compared to those for the other rare earth-gold (R-Au) systems. A short discussion of the general alloying behavior of the “coinage metals” (Cu, Ag, and Au) with the rare-earth metals is finally presented.     

Microstructure and high-temperature tensile deformation of tiai(si) alloys made from elemental powders

Two ternary TiAl-based alloys with chemical compositions of Ti-46.4 at. pct Al-1.4 at. pct Si (Si poor) and Ti-45 at. pct Al-2.7 at. pct Si (Si rich), which were prepared by reaction powder processing, have been investigated. Both alloys consist of the intermetallic compounds y-TiAl, α₂-Ti₃Al, and ξ-Ti₅(Si, Al)₃. The microstructure can be described as a duplex structure(i.e., lamellar γ/α₂ regions distributed in γ matrix) containing ξ precipitates. The higher Si content leads to a larger amount of ξ precipitates and a finer y grain size in the Si-rich alloy. The tensile properties of both alloys depend on test temperature. At room temperature and 700 °C, the tensile properties of the Si-poor alloy are better than those of the Si-rich alloy. At 900 °C, the opposite is true. Examinations of tensile deformed specimens reveal ξ-Ti₅(Si, Al)₃ particle debonding and particle cracking at lower test temperatures. At 900 °C, nucleation of voids and microcracks along lamellar grain boundaries and evidence for recovery and dynamic recrystallization were observed. Due to these processes, the alloys can tolerate ξ-Ti₅(Si, Al)₃ particles at high temperature, where the positive effect of grain refinement on both strength and ductility can be utilized.     

The ternary phase diagram,Fe-Ni-P

In order to provide the necessary phase equilibria data for understanding the development of the Widmanstatten pattern in iron meteorites, we have redetermined the Fe-Ni-P phase diagram from 0 to 100 pct Ni, 0 to 16.5 wt pct P, in the temperature range 1100° to 550°C. Long term heat treatments and 130 selected alloys were used. The electron microprobe was employed to measure the composition of the coexisting phases directly. We found that the fourphase reaction isotherm, where α+ liq ⇌ γ+ Ph, occurs at 1000° ± 5°C. Above this temperature the ternary fields α+ Ph + liq and α+ γ+ liq are stable and below 1000°C, the ternary fields ⇌+ γ + Ph and γ + Ph + liq are stable. Below 875°C a eutectic reaction, liq → γ + Ph, occurs at the Ni-P edge of the diagram. Altogether nineteen isotherms were determined in this study. The phase boundary compositions of the two-and three-phase fields are listed and are compared with the three binary diagrams. The α + γ + Ph field expands in area in each isotherm as the temperature decreases from 1000°C. Below 800°C the nickel content in all three phases increases with decreasing temperature. The phosphorus solubility in α and γ decreases from 2.7 and 1.4 wt pct at 1000°C to 0.25 and 0.08 wt pct at 550°C. The addition of phosphorus to binary Fe-Ni greatly affects the α/α + γ and γ/α + γ boundaries below 900°C. It stabilizes the α phase by increasing the solubility of nickel (α/α +γ boundary) and above 700°C, it decreases the stability field of the γ phase by decreasing the solubility of nickel(@#@ γ/α + γ boundary). However below 700°C, phosphorus reverses its role in γ and acts as a γ stabilizer, increasing the nickel solubility range. The addition of phosphorus to Fe-Ni caused significant changes in the nucleation and growth processes. Phosphorus contents of 0.1 wt pct or more allow the direct precipitation ofa from the parent γ phase by the reaction γ ⇌ α + γ. The growth rate of the α phase is substantially higher than that predicted from the binary diffusion coefficients. Formerly at Planetology Branch, Goddard Space Flight Center