The tantalum-palladium constitution diagram

The Ta-Pd system was investigated over the entire composition range by metallography, X-ray diffraction and electron microprobe analysis. The solubility limits of terminal and intermediate phases and solidus temperatures were determined. α-Ta dissolved ∼20 at. pct Pd at 2550°C and ∼10 at. pct Pd at 1000°C; α-Pd dissolves ∼22 at. pct Ta at 1730°C and ∼18 at. pct Ta at 1000°C. The presence of four intermediate phases a, (β-U type), α-TaPd (TiCu type), TaPd₂ (MoPt₂ type), and TaPd₃ (TiAl₃ type) was confirmed; they melt or decompose (α-TaPd) at about 2550, 1410; 1800, and 1770°C, respectively. In addition, an equiatomic high temperature phase, β-TaPd was found which melts at ∼1720°C and may be an extension of and isomorphous with the α-Pd solution. Seven three-phase reactions are described. Formerly with Massachusetts Institute of Technology     

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.     

Crystallization behavior of iron-containing intermetallic compounds in 319 aluminum alloy

The crystallization behavior of iron-containing intermetallic compounds in industrial grade 319 aluminum alloy has been investigated by means of thermal analysis and metallography. In the absence of manganese, the iron compound crystallizes in theβ phase, at all cooling rates ranging from 0.1 °C/s to 20 °C/s under normal casting temperatures (750 °C). However, when the melt is superheated to a high temperature (about 200 to 300 degrees above the liquidus temperature), the iron compound crystallizes in the α phase at high cooling rates. This is due to the fact that γ alumina, which forms at low melt temperatures (≤750 °C), acts as a nucleus for crystallization ofβ phase. When the melt is superheated to high temperature (≥85O °C), the γ alumina transforms to a alumina. This is a poor nucleus for the β-phase crystallization, and as a result, a phase forms. The importance of nucleation and growth undercooling for the crystallization of iron compounds is highlighted. In the presence of manganese, the iron compound crystallizes in a phase at low cooling rates and in both the α andβ phases at high cooling rates. This reverse crystallization behavior is explained in terms of phase diagram relationships.     

Effect of melt spinning on the microstructure and mechanical properties of three Ni-base superalloys

A microstructural and mechanical analysis was performed on three rapidly solidified nickel base superalloys. Transmission and scanning electron microscopy along with tensile tests were performed on the ribbons in the as-cast and aged condition. This investigation permitted a correlation to be made between cooling rate, microstructure, and mechanical properties. It was found that melt spinning significantly altered the physical characteristics of the alloys studied. The rapid cooling rates (∼10⁷ K/s) produced ribbons with a low dislocation density and small (∼1 μm) low angle cells. The precipitation of γ′ was suppressed, producing alloys with a smaller volume fraction of precipitates and lower APBE than in the conventionally cast condition. Also, the matrix/precipitate lattice mismatch was higher in the melt spun foils. Tensile strengths were similar to those in the conventional form; however, no measurable ductility was present. Aging the ribbons resulted in increases in γ′ volume fraction, tensile strengths, APBE, and elongations compared to the as-cast ribbons. The results of this work suggest that many of the microstructural refinements produced by melt spinning are lost after a short aging time at moderate temperatures.     

Crystallization kinetics of amorphous magnesium-rich magnesium-copper and magnesium-nickel alloys

Amorphous magnesium-rich alloys Mg _y X_1-y (X=Ni or Cu and 0.82<y<0.89) have been produced by melt spinning. The crystallization kinetics of these alloys have been determined by in situ X-ray diffraction (XRD) and isothermal and isochronal differential scanning calorimetry (DSC) combined with ex situ XRD. Microstructure analysis has been performed by means of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Crystallization of the Mg-Cu alloys at high temperature takes place in two steps: primary crystallization of Mg, followed by simultaneous crystallization of the remaining amorphous phase to Mg and Mg₂Cu. Crystallization of the Mg-Cu alloys at low temperatures takes place in one step: eutectic crystallization of Mg and Mg₂Cu. Crystallization of the Mg-Ni alloys for a Mg content, y>0.85, takes place in two steps: primary crystallization of Mg and of a metastable phase (Mg_∼5.5Ni, with Mg content y=0.85), followed by the decomposition of Mg_∼5.5Ni. Crystallization of the Mg-Ni alloys for a Mg content y<0.85 predominantly takes place in one step: eutectic crystallization of Mg and Mg₂Ni. Within the experimental window applied (i.e., 356 K<T<520 K and 0.82<y<0.89), composition dependence of the crystallization sequence in the Mg-Cu alloys and temperature dependence of the crystallization sequence in the Mg-Ni alloys has not been observed.     

Phase transformation during annealing of rapidly solidified Al- rich Al- Fe- Si alloys

Thermal decomposition of rapidly solidified microstructure of three Al-Fe-Si alloys (Al-10,12, 14Fe-2Si wt pct) has been studied by DTA and TEM. The initial microstructure consists mostly of aluminum and a smaller volume fraction of an amorphous phase. During heating the amorphous phase first transforms to the metastable α(AlFeSi) cubic phase (Im ,a = 1.25 nm) at ∼ 380°C. At higher temperature ∼ 430 °C the α(AlFeSi) phase transforms by ordering to a trigonal phase (two modifications, α′ and α ″,were found). The crystallography of the α′(AlFeSi) and α″(AlFeSi) phases is analyzed using selected area and convergent beam electron diffraction technique.     

On the fracture and fatigue properties of Mo-Mo<Subscript>3</Subscript>Si-Mo<Subscript>5</Subscript>SiB<Subscript>2</Subscript> refractory intermetallic alloys at ambient to elevated temperatures (25 °C to 1300 °C)

The need for structural materials with high-temperature strength and oxidation resistance coupled with adequate lower-temperature toughness for potential use at temperatures above ∼1000 °C has remained a persistent challenge in materials science. In this work, one promising class of intermetallic alloys is examined, namely, boron-containing molybdenum silicides, with compositions in the range Mo (bal), 12 to 17 at. pct Si, 8.5 at. pct B, processed using both ingot (I/M) and powder (P/M) metallurgy methods. Specifically, the oxidation (“pesting”), fracture toughness, and fatigue-crack propagation resistance of four such alloys, which consisted of ∼21 to 38 vol. pct α-Mo phase in an intermetallic matrix of Mo₃Si and Mo₅SiB₂ (T₂), were characterized at temperatures between 25 °C and 1300 °C. The boron additions were found to confer improved “pest” resistance (at 400 °C to 900 °C) as compared to unmodified molybdenum silicides, such as Mo₅Si₃. Moreover, although the fracture and fatigue properties of the finer-scale P/M alloys were only marginally better than those of MoSi₂, for the I/M processed microstructures with coarse distributions of the α-Mo phase, fracture toughness properties were far superior, rising from values above 7 MPa √m at ambient temperatures to almost 12 MPa √m at 1300 °C. Similarly, the fatigue-crack propagation resistance was significantly better than that of MoSi₂, with fatigue threshold values roughly 70 pct of the toughness, i.e., rising from over 5 MPa √m at 25 °C to ∼8 MPa √m at 1300 °C. These results, in particular, that the toughness and cyclic crack-growth resistance actually increased with increasing temperature, are discussed in terms of the salient mechanisms of toughening in Mo-Si-B alloys and the specific role of microstructure.     

Evolution of boride morphologies in TiAl-B alloys

The solidification of γ-TiAl alloys with relatively low (<2 at. pct) additions of boron is discussed. Binary Ti-Al alloys containing 49 to 52 at. pct Al form primary α-(Ti) dendrites from the melt, which are subsequently surrounded by γ segregate as the system goes through the peritectic reactionL + α →γ. Alloys between 45 and 49 at. pct Al go through a double peritectic cascade, forming primary β-(Ti) surrounded by α-(Ti) and eventually by γ in the interdendritic spaces. Boron additions to these binary alloys do not change the basic solidifi-cation sequence of the matrix but introduce the refractory compound TiB₂ in a variety of mor-phologies. The boride develops as highly convoluted flakes in the leaner alloys, but needles, plates, and equiaxed particles gradually appear as the B content increases above ∼1 at. pct. Increasing the solidification rate initially promotes the formation of flakes over plates/needles and ultimately gives way to very fine equiaxed TiB₂ particles in the interdendritic spaces of the metallic matrix. Furthermore, the primary phase selection in the 49 to 52 at. pct Al range changes from α-(Ti) to β-(Ti) at supercoolings of the order of 200 K. The different boride morphologies are fully characterized, and their evolution is rationalized in terms of differences in their nucleation and growth behavior and their relationship to the solidification of the inter-metallic matrix. Formerly Research Assistant, University of California-Santa Barbara (UCSB) Formerly Professor of Materials and Dean of the College of Engineering at UCSB     

Influence of interface microstructure on the strength of the transition joint between Ti-6Al-4V and stainless steel

Solid-state diffusion bonding of Ti-6Al-4V and type 304 SS was investigated in the temperature range of 750 °C to 950 °C, under a uniaxial load for 5.4 ks in vacuum. The diffusion bonds were characterized using light and scanning electron microscopy. The scanning electron microscopic images in backscattered mode show the existence of different reaction layers in the diffusion zone. The composition of these layers was determined by energy-dispersive X-ray spectroscopy (EDS) to contain the α-Fe, χ, λ, FeTi, β-Ti, and Fe₂Ti₄O phases. The presence of these intermetallics was confirmed by X-ray diffraction. The bond strength was evaluated, and the maximum tensile strength of ∼342 MPa and the maximum shear strength of ∼237 MPa were obtained for the diffusion couple processed at 800 °C due to the finer width of the brittle intermetallic layers. With a rise in joining temperature, the bond strength drops owing to an increase in the width of the reaction layers. The activation energy and growth constant were calculated in the temperature range of 750 °C to 950 °C for the reaction products. The χ phase showed the fastest growth rate. A fracture-surface observation in a scanning electron microscope (SEM) using EDS demonstrates that failure takes place mainly through the β-Ti phase for the diffusion couples processed in the aforementioned temperature range.     

Quantitative analysis on boundary sliding and its accommodation mode during superplastic deformation of two-phase Ti-6Al-4V alloy

A study has been made to investigate boundary sliding and its accommodation mode with respect to the variation of grain size and α/β volume fraction during superplastic deformation of a two-phase Ti-6Al-4V alloy. A load relaxation test has been performed at 600 °C and 800 °C to obtain the flow stress curves and to analyze the deformation characteristics by the theory of inelastic deformation. The results show that grain matrix deformation (GMD) is found to be dominant at 600 °C and is well described by the plastic state equation. Whereas, at 800 °C, phase/grain boundary sliding (P/GBS) becomes dominant and is fitted well with the viscous flow equation. The accommodation mode for fine-grained microstructures (3 μm) well agrees with the isostress model, while that for large-grained structures (11 μm) is a mixed mode of the isostress and isostrain-rate models. The sliding resistance analyzed for the different boundaries is lowest in the α/β boundary, and increases on the order of α/β≪α/α≈β/β, which plays an important role in controlling the superplasticity of the alloys with various α/β phase ratios.     

Texture evolution and mechanical anisotropy in dual-phase Ti<Subscript>3</Subscript>Al-based alloy loaded at 700 °C to 1000 °C

The super α ₂ Ti₃Al-based alloy with a fine grain size of ∼2.2 μm exhibits superplastic elongations over 1000 pct at 920 °C to 1000 °C, 600 pct at 900 °C, 330 pct at 850 °C, and 140 pct at 750 °C. Mechanical anisotropy is observed in this alloy, and relatively lower flow stresses and higher tensile elongations are obtained in the 45 deg specimen loaded at 25 °C to 960 °C. The texture characteristics appear to impose significant influence on the mechanical anisotropy at temperatures below 900 °C (under the dislocation creep condition), and the {111}〈2 〉 and {0001} basal textures evolve in the β and α ₂ phases after tensile straining. At loading temperatures higher than 900 °C (under the superplastic flow condition), the anisotropy effect is less pronounced and the grain orientation distribution becomes basically random in nature. Rationalizations for the mechanical anisotropy in terms of the Schmid factor calculations for the major and minor texture components in the β and α ₂ phases provide consistent explanations for the deformation behavior at lower temperatures as well as the initial straining stage at higher temperatures.     

Role of cold work and SiC reinforcements on the β′/β precipitation in Al-10 pct Mg alloy

Elevated temperature (above 100 °C) precipitation behaviors were studied in A1-10 wt pct Mg alloy and the same alloy reinforced with SiC particles through electrical resistivity, hardness, differential scanning calorimetry (DSC), and microscopy. Two distinct hardness peaks/resistivity drops, as associated with two precipitation events, were identified: (1) α (solid solution) → β′ (metastable hex precipitate) → β (Al₃Mg₂, stable complex cubic precipitate); and (2) α → β. Equilibrium β precipitates, transformed from metastable β′, were observed to possess a wide variet of orientation relationships with the matrix and were often observed to be twinned. A more restricted orientation relationship (only three variants) between β and matrix was observed in direct decomposition of α to β, and β precipitates, within these orientation relationships, were never observed to be twinned. In a predominantly binary Al-Mg system, direct precipitation of β was observed to dominate. However, the presence of trace amounts of boron nitride and/or boron (or a large supply of matrix dislocations) either from cold work, or (as in case of composites) from the thermal mismatch between the SiC and Al matrix, produced both precipitation events with event 1 dominant.     

Influence of pressing speed on microstructural development in equal-channel angular pressing

The influence of pressing speed in equal-channel angular (ECA) pressing was investigated using samples of pure Al and an Al-1 pct Mg alloy and a range of pressing speeds from ∼10⁻² to ∼10 mm s⁻¹. The results show that the speed of pressing has no significant influence on the equilibrium grain size, at least over the range used in these experiments. Thus, the equilibrium grain sizes were ∼1.2 μm for pure Al and ∼0.5 μm for the Al-1 pct Mg alloy for all pressing conditions. However, it is shown that the nature of the microstructure is dependent on the pressing speed, because recovery occurs more easily at the slower speeds, so that the microstructure is then more equilibrated. There is also indirect evidence for the advent of frictional effects when the cross-sectional dimensions of the samples are at or below ∼5 mm.     

Mechanisms of Hf dopant incorporation during the early stage of chemical vapor deposition aluminide coating growth under continuous doping conditions

A laboratory-scale chemical vapor deposition (CVD) reactor was used to perform “continuous” Hf doping experiments while the surface of a single-crystal Ni alloy was being aluminized to form an aluminide (β-NiAl) coating matrix for 45 minutes at 1150 °C. The continuous doping procedure, in which HfCl₄ and AlCl₃ were simultaneously introduced with H₂, required a high HfCl₄/AlCl₃ ratio (>∼0.6) to cause the precipitation of Hf-rich particles (∼0.1 μm) at grain boundaries of the coating layer, with the overall Hf concentration of ∼0.05 to 0.25 wt pct measured in the coating layer by glow-discharge mass spectroscopy (GDMS). Below this ratio, Hf did not incorporate as a dopant into the growing coating layer from the gas phase, as the coating matrix appeared to be “saturated” with other refractory elements partitioned from the alloy substrate. In comparison, the Hf concentration in the aluminide coating layer formed on pure Ni was in the range of ∼0.1 wt pct, which was close to the solubility of Hf estimated for bulk NiAl. Interestingly, the segregation of Hf and the formation of a thin γ′-Ni₃Al layer (∼0.5 μm) at the coating surface were consistently observed for both the alloy and pure-Ni substrates. The formation of the thin γ′-Ni₃Al layer was attributed to an increase in the elastic strain of the β-NiAl phase, associated with the segregation of Hf as well as other refractory alloying elements at the coating surface. This phenomenon also implied that the coating layer was actually growing at the interface between the γ′-Ni₃Al layer and the β-NiAl coating matrix, not at the gas/coating interface, during the early stage of the coating growth.     

Phase and structural transformations in production of powders of intermetallic compounds

The mechanism and kinetics for the formation processes of powders of intermetallic compounds when the mixtures of oxides, metals, and calcium hydride are heated in the range t = 900–1200°C (the calcium hydride method) are investigated. It is established experimentally that the compounds are synthesized in two stages. At the first stage, metal oxides are reduced by the calcium melt (starting from ∼840°C); at the second stage, diffusion interactions of the components proceed. It is shown that, for the effective development of processes of alloy formation, metal components should be dissolved in liquid calcium or to form the eutectics between one another at a value of t not exceeding the working temperature of the process. As the latter increases, the reduction of oxides and diffusion interaction between the components are intensified and finished at t < 1200°C with the formation of homogeneous powders of intermetallic compounds. The possibility of forming a wide nomenclature of powders for intermetallic compounds of different applications is shown.     

Influence that nanosecond electromagnetic pulses have on the acquisition of tin and the properties of its alloys

It is established experimentally that the influence that nanosecond electromagnetic pulses (NEMPs) have on the charge melt during the carbothermic reduction of cassiterite in the Na₂CO₃-NaNO₃ medium (1: 0.3) at t = 900–950°C accelerates the formation of the metal phase by a factor of ∼2 and affects its composition. As the duration of irradiation increases to 30 min, the tin content in the crude alloy increases to ∼95%. The influence that the NEMP treatment of the bronze melt has on its physicomechanical properties is revealed. It is shown that the influence of pulses for 10–15-min increases the alloy density to 8.92 g/cm³, hardness by a factor of 1.24, and thermal conductivity by a factor of 2.     

Microstructural evolution of a nanocrystalline Ti-47Al-3Cr alloy during annealing in the α + γ-phase field

Prealloyed, gas-atomized (GA) Ti-47Al-3Cr alloy powder, containing about 70 pct of the α ₂ (Ti₃Al) phase and 30 pct of the γ (TiAl) phase, was fully amorphized by mechanical alloying. The amorphous phase was stable during heating to 600 °C, but decomposed at higher temperatures, with an exothermic reaction peak at 624 °C as the material transformed to a mixture of α ₂ and γ and then to a fully γ structure at 722 °C. A nanocrystalline compact with a mean grain size of 42 nm was obtained by hot isostatic pressing (HIP’ing) of the amorphous powder at 725 °C. Isothermal annealing experiments were conducted in the two-phase α+γ field, at 1200 °C, using holding times of 5, 10, 25, and 35 hours, followed by air cooling. The X-ray diffractometry and analytical transmission electron microscopy investigations carried out on annealed and air-cooled specimens revealed only the presence of the γ grains, which coarsened on annealing. Initially, the grains grew, followed by a saturation stage after annealing for 25 hours, with a saturation grain size of about 1 μm. This grain growth and saturation behavior can be described with a normal grain growth mechanism in which a permanent pinning force is taken into account. Twins formed in the γ grains as a result of annealing and air cooling and exhibited a common twinning plane of (111) with the matrix phase. The minimum γ grain size in which twinning occurred in the annealed specimens was determined to be 0.25 μm, which suggests that twinning is energetically unfavorable in the nanometer-sized grains.     

Microstructure evolution in tial alloys with b additions: Conventional solidification

Solidification microstructures of arc-melted, near-equiatomic TiAl alloys containing boron additions are analyzed and compared with those of binary Ti-Al and Ti-B alloys processed in a similar fashion. With the exception of the boride phase, the matrix of the ternary alloy consists of the same α₂ (DO₁₉) and γ (Ll₀) intermetallic phases found in the binary Ti-50 at. pct Al alloy. On the other hand, the boride phase, which is TiB (B27) in the binary Ti-B alloys, changes to TiB₂ (C32) with the addition of Al. The solidification path of the ternary alloys starts with the formation of primary α (A3) for an alloy lean in boron (∼1 at. pct) and with primary TiB₂ for a higher boron concentration (∼5 at. pct). In both cases, the system follows the liquidus surface down to a monovariant line, where both α and TiB₂ are solidified concurrently. In the final stage, the α phase gives way to γ, presumably by a peritectic-type reaction similar to the one in the binary Ti-Al system. Upon cooling, the α dendrites order to α₂ and later decompose to a lath structure consisting of alternating layers of γ and α₂.