Intermetallic-reinforced light-metal matrix in-situ composites

Transition-metal trialuminide intermetallics such as Al₃Zr and Al₃Ti, having low densities and high elastic moduli, are good candidates for the in-situ reinforcement of light-metal matrices based on Al and Mg alloys. In this work, in-situ composites based on Al and Al-Mg matrices reinforced with an Al₃Zr intermetallic were successfully processed by conventional ingot metallurgy. The microstructural studies showed that “needle” or “feathery”-like particles of Al₃Zr phase, whose volume fraction increased with increasing concentration of Zr, were formed in the Al matrix in the investigated range of Zr contents from 0.9 to 11.6 at. pct. Properties of Al-Zr alloys were investigated as a function of volume fraction of Al₃Zr. It is shown that the density, hardness, and yield strength of the in-situ Al/Al₃Zr composites can be quite adequately described by the composite rule-of-mixtures (ROM) behavior. Alloying of a binary Al-2.4 at. pct Zr alloy with Mg up to ∼25 at. pct reduces profoundly its density and, additionally, strengthens the matrix by a Mg solid-solution strengthening mechanism.     

Reactive hot pressing of nonstoichiometric uranium dioxide

High density UO_2+x pellets have been produced by reactive hot pressing uranyl oxalate at temperatures up to 700°C. Rapid densification occurred during the decomposition reactions resulting in densities in the range 90 to 92 pct of the theoretical. A density of 98 pct of the theoretical value was achieved by further hot-pressing at 650° to 700°C for 30 min. This densification behavior can be related to the nonstoichiometry and submicron sized particles of UO_2+x produced in the decomposition reactions. The kinetics of hot-pressing of powder compacts of this UO_2+x were studied in the temperature range 500° to 700°C. The results were analyzed utilizing models proposed by Fryer. The activation energy of 53 kcal per mole, obtained from this analysis is the same as that for creep of nonstoichiometric urania in the temperature range 975° to 1400°C, suggesting that the mechanism controlling the rate of the final stage of densification may be a creep process.     

Processing and Characterization of Cu-Al-Ni Shape Memory Alloy Strips Prepared from Prealloyed Powder by Hot Densification Rolling of Powder Preforms

The present work deals with the preparation of near-full density Cu-Al-Ni shape memory alloy (SMA) strips from argon-atomized prealloyed powder via a powder metallurgy (PM) route comprising cold die compaction to prepare powder preforms, sintering, and hot densification rolling of unsheathed sintered powder preforms under protective atmosphere at 1273 K (1000 °C). It has been shown that argon-atomized spherical Cu-Al-Ni SMA powder consisted of very fine equiaxed grains and no appreciable grain growth occurred during sintering at 1273 K (1000 °C). It also has been shown that no appreciable densification occurred during sintering, and densification was primarily achieved by hot rolling. The densification behavior of the sintered powder preforms during hot rolling was discussed. The hot-rolled Cu-Al-Ni strips were heat-treated at 1223 K (950 °C) for 60 minutes and water quenched. The heat-treated strips consisted of equiaxed grains with average size approximately 90 μm. The heat-treated Cu-Al-Ni SMA strips consisted of self-accommodated b₁^￠ \beta_{1}^{'} martensite primarily, and showed smooth b₁ T b₁^￠ \beta_{1} \Rightarrow \beta_{1}^{'} transformation behavior coupled with a very low hysteresis (≈25 K (25 °C)). The heat-treated strips exhibited an extremely good combination of mechanical properties with fracture strength of 530 MPa and 12.3 pct fracture strain. The mode of fracture in the finished strip was primarily void-coalescence-type ductile together with some brittle transgranular type. The shape memory tests showed almost 100 pct one-way shape recovery after 100 bending-unconstrained heating cycles at 4 pct applied prestrain, exhibiting good stability of Cu-Al-Ni strips under thermomechanical actuation cycling. The two-way shape memory strain was found approximately 0.45 pct after 15 training cycles at 4 pct training strain.     

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     

Phase Diagrams of the Zr–Si–RE (RE=La and Er) Ternary Systems at 773?K (500?°C)

The isothermal sections of the phase diagram of the Zr–Si–RE (RE=La and Er) systems at 773 K (500 °C) have been investigated using X-ray power diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy (OM) with the aid of metallographic analysis. The existences of 10 binary compounds, namely ZrSi₂, α-ZrSi, α-Zr₅Si₄, Zr₃Si₂, Zr₂Si, RESi₂, RESi_2–x , RESi, RE₅Si₄, and RE₅Si₃ have been confirmed in the Zr–Si–RE (RE=La and Er) systems, respectively. As for the reported binary compound RE₃Si₂, only La₃Si₂ has been observed in the Zr–Si–La system, whereas Er₃Si₂ was not found. No binary compound was found in the Zr–RE binary systems, and no ternary compound was found in the current ternary systems. None of the phases in Zr–Si–La system reveals a remarkable solid solution at 773 K (500 °C). However, the maximum solid solubility of Zr in Er, Er₅Si₃, Er₅Si₄, ErSi, ErSi_1.67, and ErSi₂ is determined to be approximately 12.0 at. pct, 2.4 at. pct, 3.0 at. pct, 3.3 at. pct, 2.2 at. pct, and 1.8 at. pct, respectively. The maximum solid solubility of Er in ErSi₂ is approximately 1.8 at. pct. No remarkable solid solubility of the elements in any of the other phases has been observed.     

Oxidation behavior and transmission electron microscope characterization of Ti-44Al-x Nb-2(Ta,Zr) alloys

Quaternary additions of 2 at. pct of Ta or Zr were made to the ternary Ti-44Al-xNb (X=9 and 11) alloys to study the oxidation behavior at 900 °C, 950 °C, and 1000 °C for a period of 1 week. The Ta addition improves the oxidation resistance, while it is degraded by Zr compared to the ternary alloys. Identification of the oxides formed in the scale has been characterized by energy-dispersive atomic X-ray (EDAX) in a scanning electron microscope (SEM). The transmission electron microscope (TEM) analysis of the microstructures developed during oxidation has been compared with Ti-44Al-xNb alloys in order to determine the influence of quaternary additions of Ta and Zr on the phase transformations taking place during the extended period of heating. The formation of spotty α ₂ in the isolated γ grains appears to be associated with the inferior oxidation resistance of xNb2Zr alloys. This article is based on a presentation made in the symposium entitled “Fundamentals of Structural Intermetallics,” presented at the 2002 TMS Annual Meeting, February 21–27, 2002, in Seattle, Washington, under the auspices of the ASM and TMS Joint Committee on Mechanical Behavior of Materials.     

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.     

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     

Elevated temperature deformation behavior of a dispersion-strengthened Al-Fe,V,Si alloy

The deformation behavior of a rapidly solidified, dispersion-strengthened Al alloy containing 11.7 pct Fe, 1.2 pct V, and 2.4 pct Si was studied at test temperatures up to 450 °C using constantstress creep and constnt strain-rate tensile tests. Apparent stress exponents (n) up to ∼24 and an activation energy of 360 kJ/mol were obtained with the standard Arrhenius type power-law creep equation, which also suggested a change in behavior at ∼300 °C. Substructure-invariant and dislocation/dispersoid interaction models were found to be inadequate for explaining the behavior. When the data were replotted as vs σ, two regimes were found between 350 °C and 450 °C. A model with a pseudothreshold stress (σ _Th′ ) for the higher stress regime resulted inn ∼3, indicating solute drag in this regime. Transmission electron microscopy (TEM) showed departureside pinning of dislocations at higher stresses. In the lower stress regime, TEM showed dislocation subgrain structures. Here, the model resulted in a stress exponent of ∼4.5 indicating the dislocation climb mechanism. At temperatures below ∼300 °C, a single regime was found along with lower activation energies and a stress dependence of ∼3. Dislocation pipe diffusion is proposed to explain the lower activation energy. The origin ofσ _Th′ has been tied to dislocation generation at the grain boundaries.     

Ductile Ti-Based Bulk Metallic Glasses with High Specific Strength

Ti-based bulk metallic glasses (BMGs) with large compressive plasticity were developed in the Ti-rich part of Vitreloy series BMGs (Ti_65–x Zr _x Cu₉Ni₈Be₁₈ alloys with x = 0, 5, 10, 15, and 20). The current materials exhibit high fracture strength reaching ~2.3 GPa and plastic strains up to ~8.3 pct after partial substitution of Zr by Ti. The plasticity of the investigated alloys strongly depends on the Zr content, which affects the elastic constants, such as Poisson’s ratio and shear modulus. This, in turn, has an impact on the shear transformation zone (STZ) volume and, hence, on the shear banding of the glasses.     

Experimental Determination of the Liquidus in the High-Basicity Region in the Al2O3(25?mass?pct)-CaO-MgO-SiO2 and Al2O3(35?mass?pct)-CaO-MgO-SiO2 Systems

Liquidus in the Al₂O₃(25 mass pct)-CaO-MgO-SiO₂(<20 mass pct) and Al₂O₃(35 mass pct)-CaO-MgO-SiO₂(<20 mass pct) systems were determined experimentally in the high-CaO-containing region at 1873 K (1600 °C). For the Al₂O₃(35 mass pct)-CaO-MgO-SiO₂(<20 mass pct) system, liquidus data were also determined for 1773 K (1500 °C). The equilibrating and quenching technique with subsequent electron probe microanalyzer (EPMA) microanalysis were employed. Based on the data, liquidus lines were constructed for the 25 and 35 mass pct alumina planes at silica contents generally below 20 mass pct. The current results showed a slightly lower solubility of CaO and a higher solubility of MgO at 1873 K (1600 °C) for the 25 mass pct Al₂O₃ section compared with the existing phase diagram. At 1773 K (1500 °C), the result showed a slightly lower solubility of both CaO and MgO in the 35 mass pct Al₂O₃ section compared with the existing phase diagram. In addition, the activities of MgO, CaO, and Al₂O₃ were estimated at 1773 K and 1873 K (1500 °C and 1600 °C) using the phase diagram information.     

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.     

Precipitation of heusler phase (Ni<Subscript>2</Subscript>TiAl) from B2-TiNi in Ni-Ti-Al and Ni-Ti-Al-X (X=Hf,Zr) alloys

The precipitation of Heusler phase (L2₁: Ni₂TiAl) from a supersaturated B2 (TiNi-based) matrix at 600°C and 800°C is studied using transmission electron microscopy (TEM), analytical electron microscopy (AEM), and three-dimensional atom-probe (3DAP) microscopy in Ni-Ti-Al and Ni-Ti-Al-X (X=Hf and Zr) alloys. The B2/L2₁ two-phase system, with ordered structures based on the bcc lattice, is chosen for its microstructural analogy to the classical γ/γ′ system with an fcc lattice. Knowledge of the temperature-dependent partitioning of alloying elements and their atomic volumes in the B2-TiNi and L2₁ phases is desired to support design of high-performance shape-memory alloys (SMAs) with controlled misfit strain and transformation temperatures. After aging at 600°C for up to 2000 hours, the L2₁ precipitates remain fully coherent at a particle diameter of ∼20 nm. The observed effects of a misfit strain of −1.9 pct on the microstructure of the B2/L2₁ system are similar to those theoretically predicted and experimentally observed for the γ/γ′ system. The similarities are demonstrated in terms of the precipitate shape, spatial distribution, and minimum distance of separation between L2₁ precipitates. However, all these effects disappear after aging the alloys at 800°C for 1000 hours, when the L2₁ precipitates become semicoherent at particle diameters above ∼400 nm. A simple analysis of the size evolution of L2₁ precipitates after an isochronal aging (1000 hours) experiment suggests that they follow coarsening kinetics at 600°C and growth kinetics at 800°C, consistent with the Langer-Schwartz theory of precipitation kinetics, which predicts that a high supersaturation suppresses the growth regime. Microanalysis using AEM and 3DAP microscopy define the TiNi-Ni₂TiAl phase boundaries at 800°C and 600°C. At 800°C, Hf and Zr partition to the B2-TiNi, while at 600°C, they partition slightly to the L2₁ phase, reducing the lattice misfit to −1.7 and −0.011 pct, respectively, and partition strongly to the metastable phase Ti₂Ni₃. To describe the composition dependence of the lattice parameter of multicomponent B2 and L2₁ phases, the atomic volumes of Al, Hf, Ni, Ti, and Zr in the B2-TiNi and L2₁ phases are determined. A simple model is proposed to predict the lattice parameters of these phases in multicomponent systems.     

Toward Oxidation-Resistant ZrB<Subscript>2</Subscript>-SiC Ultra High Temperature Ceramics

Ultra high temperature ceramics (UHTCs), including ZrB₂-SiC, are designed for extreme environment applications in which temperatures exceed 2273 K (2000 °C). A key material property of UHTCs in many applications is their resistance to oxidation. Recent research into UHTCs is described, revealing a variety of different methods for improving the oxidation performance, which include control of starting powders, composition and size distribution, mixing, and densification techniques. The use of additives has also been researched widely, for example, to increase the viscosity of any liquid phase formed or provide protective refractory phases at high temperatures. SiC additions are effective in forming protective silica but only in static environments and to ~1873 K (1600 °C). For higher temperature applications, additions of La lead to the formation of a dense ZrO₂ scale probably via liquid phase sintering. Such ceramic systems, which produce self-generating refractory oxidation barriers or dense ZrO₂ scales, show the greatest promise in providing oxidation-resistant UHTCs.     

Solidification paths and carbide morphologies in melt-processed MoSi2-SiC In Situ composites

The present investigation was undertaken to elucidate the microstructural evolution of MoSi₂-SiC in situ composites produced by melt processing. An assessment of the existing liquidus projection was performed by a combination of thermodynamic modeling, analysis of solidification microstructures, and measurements of the thermal history during solidification. Results show that the quasibinary MoSi₂-SiC eutectic occurs at ∼2 at. pct C and 2283 K, rather than 8 at. pct C and 2173 K, as previously reported. The ensuing L+MoSi₂+SiC monovariant line runs almost parallel to the SiMoSi₂ binary and terminates at a ternary L ↔ Si+MoSi₂+SiC eutectic calculated at 1.5Mo-0.84C (at. pct) and ∼1670 K. The maximum amount of SiC that may be produced by solidification along the quasibinary isopleth is ∼37 vol pct, of which ∼35 vol pct grows as primary. Analysis of solidification microstructures shows SiC grows with the cubic β polytype structure (B3), while MoSi₂ grows with the tetragonal C11 _b structure. Primary SiC may grow as equiaxed particles, platelets, and hopper crystals. Coupled growth with MoSi₂ leads to SiC in the shape of thin ribbons, sheets, and needles. The facets of the SiC crystals were identified to be of the {111} and {002} type, in agreement with the periodic bond chain analysis. The predominant platelike morphology was shown to develop due to a re-entrant twin mechanism similar to that observed in Si and Ge.     

The Kinetics of the Nitriding of Ternary Fe-2 at pct Cr-2 at pct Ti Alloy

The mechanism and the kinetics of growth of the nitrided zone of ternary Fe-2 at pct Cr-2 at pct Ti alloy was investigated by performing gaseous nitriding experiments at temperatures of 833 K and 853 K (560 °C and 580 °C) and at nitriding potentials r _N = 0.004 atm^−1/2 and 0.054 atm^−1/2. The microstructure of the nitrided zone was investigated by transmission electron microscopy and the elemental compositional variation with depth was determined by employing electron probe microanalysis. Fine platelet-type mixed Cr_{1 – x} Ti _x N nitride precipitates developed in the nitrided zone. To describe the evolution of the nitrogen concentration depth profile, a numerical model was developed with the following parameters: the surface nitrogen content, the solubility product(s) of the alloying elements and dissolved nitrogen in the ferrite matrix, and a parameter defining the composition of the inner nitride precipitates. These parameters were determined by fitting model-calculated nitrogen depth profiles to the corresponding experimental data. The results obtained demonstrate that the type of nitride formation (i.e., whether Cr and Ti precipitate separately, as CrN and TiN, or jointly, as mixed Cr_{1 – x} Ti _x N) as well as the amounts of mobile and immobile excess nitrogen taken up by the specimen considerably influence the shape and extent of the nitrogen concentration profiles.     

High-temperature phase equilibria in the Al-rich corner of the Al-Ti-C system

A thermodynamic analysis of the Al-rich corner in the ternary Al-Ti-C diagram, providing phase relations and regions of phase stability, is presented. An invariant four-phase equilibrium between Al, Al₄C₃, Al₃Ti, and TiC _x takes place at 0.53 at. pct Ti, 7.10⁻⁶ at. pct C, and TiC_0.883 at 966 K. The carbon content of the TiC _x phase, which extends from x=0.48 to 0.98, exerts a significant effect on phase relationships in this ternary system. In particular, it is shown that stoichiometric TiC is not stable in the presence of liquid Al. For example, at 1300 K, a two-phase equilibrium between Al _L and TiC _x exists only in the 0.91<x<0.82 range. Thus, the interaction of Al _L with stoichiometric TiC leads to the formation of the Al₄C₃ aluminum carbide phase, whereas for x<0.82, only the intermetallic compound Al₃Ti can form at this temperature. The results of this analysis were confirmed by X-ray diffraction (XRD) measurements of relevant composites.