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.     

Precipitation strengthening in K5-series γ-TiAl alloyed with silicon and carbon

Interstitial additions and precipitation hardening in fully lamellar gamma TiAl have been investigated in recent years, with a prime objective of improving the high-temperature creep resistance. As a result of this alloy development effort, the alloy system K5 (Ti46Al-2Cr-3Nb-0.2W) was found to show remarkably improved creep resistance when reinforced with C or C+Si additions and then aged appropriately. Precipitation strengthening is the proposed mechanism accounting for the observed creep strengthening of K5SC alloys, with emphasis being paid on the effect of B2 particles, ζ-type silicides, and H-type carbide precipitates delineating γ/γ interfaces. In this study, the creep-deformed microstructures of fully lamellar K5 (S-C)-type alloys in aged and unaged conditions were characterized using detailed electron microscopy, involving high-resolution imaging techniques and in-situ heating studies. Overall, the presence of these particles and their relative distribution result in strengthening of the lamellar structure. The particular effect of each type of precipitate (silicides vs carbides) on creep has been assessed. New information about the nature of the light-element precipitation processes has been obtained by studying the nucleation and growth of the carbide and silicide precipitates at the expense of dissolving α ₂ laths during aging. 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.     

Fundamental considerations for the development of oxidation-resistant alloys and coatings based on γ-TiAl

Alloys based on γ-TiAl are promising high-temperature materials that may replace conventional heat-resistant steels and superalloys in applications where high strength in combination with low density is required. However, an important hindrance to the use of γ-TiAl alloys at high temperatures is their relatively poor oxidation resistance and sensitivity against environmentally induced embrittlement. This material degradation is related to the poor protective properties of the mixed TiO₂/Al₂O₃ surface scales which form on the surface during high-temperature exposure. Recently, it was shown that protective alumina scale formation on γ-TiAl can be obtained by small additions of Ag. This effect was found to be related to the formation of Z phase in the subscale depletion layer at the expense of α ₂-Ti₃Al. It was found that the beneficial effect of Ag can be suppressed if the alloys contain additional α ₂-stabilizing elements, such as Nb, as is the case for most (semi)commercial, high-strength alloys. Therefore, recent efforts have concentrated on developing Ag-containing γ-TiAl alloys as oxidation-resistant coatings for high-strength titanium aluminides. Preliminary results using magnetron sputtering have shown that, due to the similarities in chemical and physical properties of the coating and base material, the Ag-containing material offers promising potential to be qualified as a coating material for reducing the oxidation-induced degradation of titanium aluminides. 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 effects on fracture toughness of ductile-phase composition and morphology in Nb-Cr-Ti and Nb-Siin situ composites

Niobium-chromium alloys, both single and two phase, were alloyed with titanium in order to enhance fracture toughness and fatigue crack growth resistance. The selection of titanium as an alloying element and the relationship of electronic bonding to toughness are examined. The results indicated that toughness increased with a decreasing number of D +s electrons. Titanium was found to increase the toughness of solid-solution Nb-Cr alloys from ≈8 to 87 MPa√m, while for the twophase “insitu composites,” toughness was increased from ≈5 to 20 MPa√m, although this is less than expected. Fracture toughness of the composites correlated nonlinearly with the volume fraction of the phases. The evidence suggests that the toughness of the composites is decreased due to fracture of the intermetallic particles and constraint on matrix deformation imposed by the intermetallic. Fracture characteristics of the Nb-Cr-Ti materials are compared to those of Nb-Cr and Nb-Si materials.     

Effect of ion implantation on the oxidation resistance of TiAl

Ion implantation was applied to a gamma TiAl alloy, and the oxidation behavior of the alloy implanted with B, P, Fe, or W was investigated through a cyclic oxidation test at 1200 K in a flow of purified oxygen under atmospheric pressure. Metallographic examinations were performed for the implanted specimens and the oxidized specimens using X-ray diffractometry (XRD), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). The β phase was detected along with γ-TiAl in the Fe- or W-implanted specimens, while γ-TiAl was the predominant phase for the B- or P-implanted specimens. The implantation of P, Fe, or W significantly improved the oxidation resistance, provided the ion dose was sufficient, whereas the implantation of B enhanced scale spallation, resulting in deteriorated oxidation resistance. The AES profiles for the specimens oxidized for a very short period strongly suggested the incorporation of P or W in TiO₂. The possible mechanisms for the improvement are discussed on the basis of the results obtained for the implanted 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.     

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.     

Creep behavior of TiAl alloys with enhanced high-temperature capability

For high-temperature applications, creep strength is of major concern, in addition to oxidation and corrosion resistance, and determines the application range of titanium aluminide alloys in competition with other structural materials. Thus, this work was aimed at identifying mechanisms of creep deformation and microstructural degradation and at developing alloying concepts with respect to an enhanced high-temperature capability. The analysis shows that dislocation climb controls deformation in the range of the intended operation temperatures. Further, complex processes of phase transformations, recrystallization, and microstructural coarsening were observed, which contribute to microstructural degradation and limit component life in long-term service. By alloying with high contents of Nb, both room- and high-temperature strength properties can be improved as Nb increases the activation energy of diffusion and increases the propensity for twinning at ambient temperature. For alloys with enhanced high-temperature capability, microalloying with carbon is also of particular use, because carbide precipitates effectively hinder dislocation motion and are thought to increase microstructural stability. 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.     

On the development and investigation of quaternary Pt-based superalloys with Ni additions

The objective of this work is to mimic the microstructure and strengthening mechanisms of Ni-based superalloys in a new group of high-temperature alloys based on the system Pt-Al. The elements Cr and Ni were chosen as further alloying components. Having a face-centered cubic (fcc) crystal structure with an Ll₂-ordered and coherently embedded phase, these new alloys should increase creep and corrosion resistance beyond Ni-based superalloys. After arc melting and heat treatment, the alloys were investigated by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). In the aged condition, the alloy composition 13 at. pct Al, 3 at. pct Cr, 7 at. pct Ni, and balance Pt showed the most promising microstructure with cubical precipitates, 30 pct precipitate volume fraction, and a lattice misfit of about −0.1 pct at room temperature. This article is based on a presentation made in the symposium entitled “Beyond Nickel-Base Superalloys,” which took place March 14–18, 2004, at the TMS Spring meeting in Charlotte, NC, under the auspices of the SMD-Corrosion and Environmental Effects Committee, the SMD-High Temperature Alloys Committee, the SMD-Mechanical Behavior of Materials Committee, and the SMD-Refractory Metals Committee.     

The balance of mechanical and environmental properties of a multielement niobium-niobium silicide-basedIn Situ composite

This article describes room-temperature and high-temperature mechanical properties, as well as oxidation behavior, of a niobium-niobium silicide basedin situ composite directionally solidified from a Nb-Ti-Hf-Cr-Al-Si alloy. Room-temperature fracture toughness, high-temperature tensile strength (up to 1200 °C), and tensile creep rupture (1100 °C) data are described. The composite shows an excellent balance of high- and low-temperature mechanical properties with promising environmental resistance at temperatures above 1000 °C. The composite microstructures and phase chemistries are also described. Samples were prepared using directional solidification in order to generate an aligned composite of a Nb-based solid solution with Nb₃Si- and Nb₅Si₃-type silicides. The high-temperature mechanical properties and oxidation behavior are also compared with the most recent Ni-based superalloys. This composite represents an excellent basis for the development of advanced Nb-based intermetallic matrix composites that offer improved properties over Ni-based superalloys at temperatures in excess of 1000 °C.     

In-Situ observations of oxidation and phase stability in cast nickel-based intermetallic alloys

The effects of the as-cast microstructure on the oxidation characteristics of two Ni-Al-Cr alloys with either γ or γ′ primary solidification were investigated with an in-situ, time-resolved X-ray diffraction (TRXRD) technique using synchrotron radiation. The measurements, carried out during rapid heating and cooling, showed that a segregated microstructure in these cast alloys leads to the preferential formation of zirconium oxide before the formation of aluminum oxides is detected. The oxidation leads to a change in the phase stability and to the modification of surface microstructures. Computational thermodynamic models were used to explain the preferential formation of oxides in the as-cast microstructure.     

Compressive strength and creep properties of Ir-Nb-Zr alloys between 1473 and 2073 K

The microstructure and strength at 1473 and 2073 K and creep properties at 2073 K were investigated in three Ir-Nb-Zr alloys with the fcc and L1₂ two-phase structure. The microstructure and lattice misfit were investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffractometry (XRD). Compression and creep tests were performed, and their deformation structures were observed using SEM and TEM. At 1473 K, the strength of the Ir-Nb-Zr alloys was higher than that of the binary Ir-Nb and Ir-Zr alloys, but they were almost equivalent at 2073 K. However, the ternary alloys showed great improvement on creep at 2073 K. The time for the 2 pct creep strain of the Ir-Nb-Zr alloy was about 100 hours, while it was 1 hour for the binary alloys. The deformation mechanisms for compressive strength and creep resistance in these Ir-Nb-Zr alloys are discussed in terms of the deformation structure. 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.     

合金化及涂层技术提高铌基合金的抗高温氧化性能

综述了铌基合金的成分设计及抗高温氧化研究的现状，对铌基合金包埋渗法制备涂层研究的进展及存在的问题进行了阐述，提出了解决铌基合金抗高温氧化性能差的可能途径。     

Effects of silicon on the oxidation,hot-corrosion,and mechanical behavior of two cast nickel-base superalloys

Cast specimens of nickel-base superalloys 713C and Mar-M200 with nominal additions of 0, 0.5, and 1 wt pct Si were evaluated for oxidation and corrosion resistance, tensile and stress-rupture properties, microstructure, and phase relations. Results are com-pared with those of an earlier study of the effects of Si in B-1900. Si had similar effects on all three superalloys. It improves oxidation resistance but the improvement in 713C and Mar-M200 was considerably less than in B-1900. Hot-corrosion resistance is also improved somewhat. Si is, however, detrimental to mechanical properties, in particular, rupture strength and tensile ductility. Si has two obvious microstructural effects. It in-creases the amount of γ precipitated in eutectie nodules and promotes a Mo(Ni,Si)₂ Laves phase in the alloys containing Mo. These microstructural effects do not appear responsible for the degradation of mechanical properties, however.     

Contribution of electrospark alloying to the oxidation resistance of hard tungsten alloys

The paper examines the contribution of electrospark alloying to the oxidation resistance of hard tungsten alloys. It is established that the oxidation of carbides results from their electronic structure. When WC and hard tungsten alloys are heated to 1000°C, a brittle scale consisting of WO₃ and CoWO₄ rapidly forms. The oxidation resistance reduces as follows: TiC → Co → W → HTA (if TiC is more than 10%) → WC-Co → WC. The oxidation rate of hard tungsten alloys may be a criterion of their serviceability. It is shown that the oxidation resistance of hard tungsten alloys becomes much higher after their electrospark alloying with aluminum, titanium, and chromium and with wear-resistant composite TsLAB-2 ceramics based on the ZrB₂-ZrSi₂-LaB₆ system with Ni-Cr-Al (30 mole%) binder. __________ Translated from Poroshkovaya Metallurgiya, Vol. 47, No. 1–2 (459), pp. 145–150, 2008.     

Fundamental aspects of creep in metal matrix composites

The primary characteristics of the creep of metal matrix composites (MMCs) are reviewed, including the shapes of the creep curves, the origin of the threshold stresses, and the nature of the rate-controlling processes. A detailed analysis of two representative MMCs provides no support for the concept of a constant substructure model for creep with a stress exponent (n) of 8. Analysis of the data demonstrates that creep is controlled by deformation in the matrix alloys and, as in solid solution alloys, there is a division into control by viscous glide (class A) and climb (class M), respectively. This article is based on a presentation made in the symposium “Fatigue and Creep of Composite Materials” presented at the TMS Fall Meeting in Indianapolis, Indiana, September 14–18, 1997, under the auspices of the TMS/ASM Composite Materials Committee.     

<Emphasis Type="Italic">In-Situ</Emphasis> High-Energy X-Ray Diffuse-Scattering Study of the Phase Transition in a Ni<Subscript>2</Subscript>MnGa Ferromagnetic Shape-Memory Crystal

The full information on the changes in many crystallographic aspects, including the structural and microstructural characterizations, during the phase transformation is essential for understanding the phase transition and “memory” behavior in the ferromagnetic shape-memory alloys. In the present article, the defects-related microstructural features connected to the premartensitic and martensitic transition of a Ni₂MnGa single crystal under a uniaxial pressure of 50 MPa applied along the [110] crystallographic direction were studied by the in-situ high-energy X-ray diffuse-scattering experiments. The analysis of the characteristics of diffuse-scattering patterns around different sharp Bragg spots suggests that the influences of some defect clusters on the pressure-induced phase-transition sequences of Ni₂MnGa are significant. Our experiments show that an intermediate phase is produced during the premartensitic transition in the Ni₂MnGa single crystal, which is favorable for the nucleation of a martensitic phase. The compression stress along the [110] direction of the Heusler phase can promote the premartensitic and martensitic transition of the Ni₂MnGa single crystal. This article is based on a presentation given in the symposium entitled “Neutron and X-Ray Studies for Probing Materials Behavior,” which occurred during the TMS Spring Meeting in New Orleans, LA, March 9–13, 2008, under the auspices of the National Science Foundation, TMS, the TMS Structural Materials Division, and the TMS Advanced Characterization, Testing, and Simulation Committee.     

Characterization and tribological behavior of cast In-Situ Al (Mg,Mo)-Al2O3 (MoO3) composite

Aluminum alloy—based cast in-situ composite has been synthesized by dispersion of externally added molybdenum trioxide particles (MoO₃) in molten aluminum at the processing temperature of 850 °C. During processing, the displacement reaction between molten aluminum and MoO₃ particles results in formation of alumina particles in situ and also releases molybdenum into molten aluminum. A part of this molybdenum forms solid solution with aluminum and the remaining part reacts with aluminum to form intermetallic phase Mo(Al_1−x Fe _x )₁₂ of different morphologies. Magnesium (Mg) is added to the melt in order to help wetting of alumina particles generated in situ, by oxidation of molten aluminum by molybdenum trioxide, and helps to retain these particles inside the melt. The mechanical properties of the cast in-situ composite, as indicated by ultimate tensile stress, yield stress, percentage elongation, and hardness, are relatively higher than those observed either in cast commercial aluminum or in cast Al-Mo alloy. The wear and friction of the resulting cast in-situ Al(Mg,Mo)-Al₂O₃(MoO₃) composites have been investigated using a pin-on-disc wear testing machine under dry sliding conditions at different normal loads of 9.8N, 14.7N, 19.6N, 24.5N, 29.4N, 34.3N, and 39.2 N and a constant sliding speed of 1.05 m/s. The results of the current investigation indicate that the cumulative volume loss and wear rate of cast in-situ composites are significantly lower than those observed either in cast commercial aluminum or in cast Al-Mo alloy, under similar load and sliding conditions. Beyond about 30 to 35 N loads, there appears to be a higher rate of increase in the wear rate in the cast in-situ composite as well as in cast commercial aluminum and cast Al-Mo alloy. For a given normal load, the coefficient of friction of cast in-situ composite is significantly lower than those observed either in cast commercial aluminum or in cast Al-Mo alloy. The coefficient of friction of cast in-situ composite increases gradually with increasing normal load while those observed in cast commercial aluminum or in cast Al-Mo alloy remain more or less the same. Beyond a critical normal load of about 30 to 35 N, the coefficient of friction decreases with increasing normal load in all the three materials.     

In-situ observations of titanium metal-matrix composites under transverse tensile loading

The transverse stress-strain behavior of several titanium metal-matrix composites (TiMMCs) has been studied in-situ. Debonding of 1140+/Ti-6-4 composites occurs over a range of stresses. The sharpness of the first “knee” is affected by the fiber volume fraction and by the relative moduli of the matrix regions and the reinforced composite. It has been observed that debonding occurs mainly at the interface between two sublayers of carbon/carbon coatings in 1140+/Ti-6-4 composites and mainly at the interface between the carbon/reaction zone in the as-processed and peak-aged 35 pct SCS-6/Tiβ21s composites. At surface positions, this process starts at very low stresses (≥50 MPa) from the positions with sharp changes of curvatures (or undulations), voids, or debris at the periphery of the interface. Cracking of the outermost carbon sublayer and of the reaction zone in the 1140+/Ti-6-4 composites and the reaction zone in the SCS-6/Tiβ21s composites occurs during elastic deformation of the matrix. This has been directly observed in a field-emission gun (FEG)-scanning electron microscope (SEM) under incremental loading. Although these cracks are arrested and blunted by the matrix material, they cause local stresses and, thus, stimulate local plastic deformation of the matrix and subsequent development of a second knee on the stress-strain curve. The in-situ observations are discussed in terms of the effects of fiber volume fraction and fiber type on the loci and dynamic processes of interfacial debonding, cracking of carbon coatings and reaction zones, and plastic deformation of the matrix.     

<Emphasis Type="Italic">In-Situ</Emphasis> Fracture Observation and Fracture Toughness Analysis of Ni-Mn-Ga-Fe Ferromagnetic Shape Memory Alloys

The fracture property improvement of Ni-Mn-Ga-Fe ferromagnetic shape memory alloys containing ductile γ particles was explained by direct observation of microfracture processes using an in-situ loading stage installed inside a scanning electron microscope (SEM) chamber. The Ni-Mn-Ga-Fe alloys contained a considerable amount of γ particles in β grains after the homogenization treatment at 1073 K to 1373 K (800 °C to 1100 °C). With increasing homogenization temperature, γ particles were coarsened and distributed homogeneously along β grain boundaries as well as inside β grains. According to the in-situ microfracture observation, γ particles effectively acted as blocking sites of crack propagation and provided the stable crack growth, which could be confirmed by the R-curve analysis. The increase in fracture resistance with increasing crack length improved overall fracture properties of the Ni-Mn-Ga-Fe alloys. This improvement could be explained by mechanisms of blocking of crack propagation and crack blunting and bridging.     

Partial phase relationships in Ir-Nb-Ni-Al and Ir-Nb-Pt-Al quaternary systems and mechanical properties of their alloys

Two quanternary systems, Ir-Nb-Ni-Al and Ir-Nb-Pt-Al, were successively investigated to assess their possible use in ultra-high-temperature applications. The phase relationships concentrated on the fcc/L1₂ two-phase region were primarily established, and the mechanical properties were studied. Ir-Nb-Ni-Al quaternary alloys around the Ir-rich or Ni-rich corners of the Ir-Nb-Ni-Al tetrahedron showed a coherent fcc/L1₂ two-phase structure, analogous to that of Ni-base superalloys; however, most of the alloys presented three or four phases with two types of L1₂ phases. Although these alloys showed a high compressive strength at high temperature, they exhibited a higher creep rate than Ir-base binary and ternary alloys. Another quanternary system, Ir-Nb-Pt-Al, showed promising results. Only an fcc/L1₂ two-phase structure was found in all the alloys investigated with compositions ranging from the Ir-rich side to the Pt-rich side, and the lattice misfit between the fcc and L1₂ phases was small. The high-temperature strength at 1200 °C of Ir-Nb-Pt-Al alloys was higher than that of Ir-Nb-Ni-Al alloys with the same Ir content (at. pct). Moreover, Ir-Nb-Pt-Al alloys exhibited excellent creep resistance at 1400 °C and 100 MPa. This article is based on a presentation made in the symposium entitled “Beyond Nickel-Base Superalloys,” which took place March 14–18, 2004, at the TMS Spring meeting in Charlotte, NC, under the auspices of the SMD-Corrosion and Environmental Effects Committee, the SMD-High Temperature Alloys Committee, the SMD-Mechanical Behavior of Materials Committee, and the SMD-Refractory Metals Committee.