Microstructures of Rene 142 nickel-based superalloy fabricated by electron beam melting

Rene 142, a commercial, columnar grained, gas turbine airfoil Ni-based superalloy, has been fabricated from a pre-alloyed, atomized powder by additive manufacturing using electron beam melting. Monolithic components having [0 0 1] oriented, columnar grain structures exhibited a creep-optimized 59% volume fraction of cuboidal, coherent, γ′-phase precipitates averaging 275 nm on the side, and with γ/γ′ channel widths ranging from 25 to 75 nm. Transmission electron microscopy, utilizing bright and dark field imaging of optimally oriented γ/γ′ interfaces showed prominent misfit coherency strains as δ-fringe patterns. Corresponding hardness measurements also indicated the possibility of creep strength comparable with the commercial alloy. The notable feature of this study was the monolithic development of desirable superalloy properties without conventional, multi-step heat treatments.     

Creep deformation of fully lamellar TiAl controlled by the viscous glide of interfacial dislocations

Creep mechanisms of fully lamellar TiAl with a refined microstructure (γ lamellae: 100–300 nm thick, α₂ lamellae: 10–50 nm thick) have been investigated. A nearly linear creep behavior (i.e. the steady-state creep rate is nearly proportional to the applied stress) was observed when the alloy was creep deformed at low applied stresses (<400 MPa) and intermediate temperatures (650–810°C). Since the operation and multiplication of lattice dislocations within both γ and α₂ lamellae are very limited in a low stress level as a result of the refined lamellar microstructure, creep mechanisms based upon glide and/or climb of lattice dislocations become insignificant. Instead, the motion of interfacial dislocation arrays on γ/α₂ and γ/γ interfaces (i.e. interface sliding) has found to be a predominant deformation mechanism. According to the observed interfacial substructure caused by interface sliding and the measured activation energy for creep, it is proposed that creep deformation of the refined lamellar TiAl in the intermediate-temperature and low-stress regime is primarily controlled by the viscous glide of interfacial dislocations.     

Lattice strain evolution during creep in single-crystal superalloys

In situ neutron diffraction studies are carried out to characterize the micromechanical deformation occurring during tensile creep of a typical single-crystal nickel-based superalloy, CMSX-4. The loading responses of the matrix γ phase and the precipitate γ′ are distinct. Moreover, the behaviour in the tertiary creep regime (in which the γ′ phase remains intact) is qualitatively different from that in the primary creep regime (when γ′ is sheared). In tertiary creep, initial deformation of the matrix leads to a release of misfit between the phases in the (1 0 0), resulting in elastic compression of the γ in the loading direction. The load state then remains fairly constant during creep. During the initial stages of primary creep, elastic compression of the γ phase is observed until at around 2–4% creep strain this compression stabilizes as the (1 0 0) misfit is released. This is the point at which γ′ shearing is thought to begin. Subsequently, the load in the γ increases by around 200 MPa until a maximum is reached at around 8% creep strain. This load is then suddenly released, which may be due to the release of back-stress.     

Development of γ phase stacking faults during high temperature creep of Ru-containing single crystal superalloys

An unusual deformation mode involving the formation of intrinsic stacking faults in the γ matrix of experimental Ru-containing γ–γ′ superalloys with high Co and Re contents during high temperature creep at 950 °C/290 MPa has been observed. The morphology, distribution and dependence of these stacking faults on alloy chemistry has been investigated along with their formation mechanism. Additions of Re and Co substantially decrease the stacking fault energy of the γ matrix. The observed stacking faults in the γ matrix form by the dissociation of a/2〈1 1 0〉 matrix dislocations with Burgers vectors perpendicular to the loading direction in the early stages of creep. The dependence of creep properties on elemental additions that influence stacking fault energy is discussed.     

Creep behaviour of a new air-hardenable intermetallic Ti–46Al–8Ta alloy

Creep behaviour of a new cast air-hardenable intermetallic Ti–46Al–8Ta (at.%) alloy was investigated. Constant load tensile creep tests were performed at initial applied stresses ranging from 200 to 400 MPa in the temperature range from 973 to 1073 K. The minimum creep rate is found to depend strongly on the applied stress and temperature. The power law stress exponent of the minimum creep rate is n = 5.8 and the apparent activation energy for creep is calculated to be Q_a = (382.9 ± 14.5) kJ/mol. The kinetics of creep deformation of the specimens tested to a minimum creep rate (creep deformation about 2%) is suggested to be controlled by non-conservative motion of dislocations in the γ(TiAl) matrix. Besides dislocation mechanisms, deformation twinning contributes significantly to overall measured strains in the specimens tested to fracture. The initial γ(TiAl) + α₂(Ti₃Al) microstructure of the creep specimens is unstable and transforms to the γ + α₂ + τ type during creep. The particles of the τ phase are preferentially formed along the grain and lamellar colony boundaries.     

Visible laser microfabrication of transparent plastic using Au nanoparticles-dispersed polymer film

A polymer film in which Au nanoparticles with average diameter of around 3 nm dispersed in ethylcellulose was applied to an absorber for laser microfabrication of a transparent plastic. Since the polymer film has a strong absorption at the wavelength of around 530 nm, it can be micromachined using focused low power Nd:YVO₄–SHG laser (CW, wavelength of 532 nm). When laser beam was irradiated on the polymer film coated on transparent substrate, the substrate under the polymer film which has no absorbance in the range of wavelength of laser beam was processed. A micropattern was clearly fabricated on transparent poly(methyl methacrylate) and polyethylene terephthalate using our polymer film. In poly(methyl methacrylate) substrate, the processed depth showed a maximum at the polymer film thickness of 15 μm under the condition of laser power of 23 mW. Finally, laser marking test on the transparent poly(methyl methacrylate) was demonstrated as an application of our system using the optimal polymer film thickness.     

A diffusion analysis of transient subsurface γ′-Ni3Al formation during β-NiAl oxidation

Cross-sectional transmission electron microscopy has demonstrated γ′-Ni₃Al formation at the alloy/oxide interface during β-NiAl (1 1 0) oxidation under specific conditions. Diffusion analysis was applied to interpret this subsurface phase formation process. It showed that thermodynamically sufficient conditions for phase formation could be achieved with increasing temperature during the early oxidation stage. To stabilize continued γ′ growth, a kinetic requirement needed to be considered, which led to a thickness criterion. The predicted extent of subsurface γ′ phase formation showed good agreement with the experimental observations.     

Tensile creep of Mo–Si–B alloys

Multiphase Mo–Si–B alloys containing a Mo solid solution matrix and brittle Mo₃Si and Mo₅SiB₂ (T2) intermetallic phases are candidates for ultra-high-temperature applications_. The elevated temperature uniaxial tensile response at a nominal strain rate of 10^?4 s^–1 and the tensile creep response at constant load between 1000 °C and 1300 °C of a (i) single phase solid solution (Mo–3.0Si–1.3B in at.%), (ii) two-phase alloy containing ～35 vol.% T2 phase (Mo–6Si–8B in at.%) and (iii) three-phase alloy with ～50 vol.% T2 + Mo₃Si phases (Mo–8.6Si–8.7B in at.%) were evaluated. The results confirm that Si in solid solution significantly enhances both the yield strength and the creep resistance of these materials. A Larson–Miller plot of the creep data showed improved creep resistance of the two- and three-phase alloys in comparison with Ni-based superalloys. The extent of Si dissolved in the solid solution phase varied in these three alloys and Si appeared to segregate to dislocations and grain boundaries. A stress exponent of ～5 for the solid solution alloy and ～7 at 1200 °C for the two multiphase alloys suggested dislocation climb to be the controlling mechanism. Grain boundary precipitation of the T2 phase during creep deformation was observed and the precipitation kinetics appear to be affected by the test temperature and applied stress.     

Bulk amorphous FC20 (Fe–C–Si) alloys with small amounts of B and their crystallized structure and mechanical properties

The addition of a small amount (0.4 mass%) of B to a commercial FC20 cast iron was found to cause the formation of an amorphous phase in melt-spun ribbon and cast cylinders with a diameter of up to 0.5 mm. The structure of a melt-spun B-free FC20 alloy consisted of α-Fe, γ-Fe and Fe₃C. The effectiveness of additional B is presumably due to the generation of attractive bonding nature among the constituent elements. The amorphous alloy ribbon exhibits a high tensile strength of 3480 MPa and good bending ductility. The annealing causes the formation of an amorphous phase containing α-Fe particles with a size of about 30 nm. The mixed phase alloy exhibits an improved tensile strength of 3800 MPa without detriment to good ductility. With further increasing temperature, the mixed amorphous and α-Fe structure changes to α-Fe+Fe₃C+graphite through the metastable structure of α-Fe+Fe₃C. The structure after annealing for 900 s at 1200 K has fine grain sizes of about 0.5 μm for α-Fe, 0.3 μm for Fe₃C and 1 μm for graphite. The graphite-containing alloy exhibits high tensile strength of 1200–2000 MPa and large elongation of 5–13%. The high tensile strength and good ductility were also obtained for the 0.5 mm cylinder annealed at 1200 K. The good mechanical properties are due to the combination of fine subdivision of crack initiation sites by the homogeneous dispersion of small graphite particles and the dispersion strengthening of Fe₃C particles against the deformation of the α-Fe phase. The synthesis of the finely mixed α-Fe+Fe₃C+graphite alloys having good mechanical properties by crystallization of the new amorphous alloy in the melt-spun ribbon and cast cylinder forms is encouraging for the future development of a new Fe-based high-strength and high-ductility material.     

Evolution of orientation distributions of γ and γ′ phases during creep deformation of Ni-base single crystal superalloys

The evolution of orientation distributions of γ and γ′ phases in crept Ni-base single crystal superalloys have been investigated by theoretical calculations with elastic–plastic models and by experiments. As creep deformation proceeds, the crystallographic orientation distributions for both phases are broadened as a result of the waving of the raft structure, which occurs to reduce the total mechanical energy. The broadening of the orientation distribution occurs in such a way that the 0 0 1 pole broadens isotropically while the h k 0 poles broaden preferentially along the 〈0 0 1〉 directions. Since the extent of the broadening increases almost linearly with the number of creep deformation, the measurement of the broadening by X-ray diffraction can be utilized in non-destructive methods to predict the lifetime of Ni-base superalloys.     

Mechanical properties of dual multi-phase single-crystal intermetallic alloy composed of geometrically close packed Ni3X (X: Al and V) type structures

Dual multi-phase intermetallic alloy, which is composed of Ni₃Al(L1₂) and Ni solid solution (A1) phases at high-temperature annealing and is additionally refined by a eutectoid reaction at low temperature aging, according to which the Al phase is transformed into the Ni₃Al(L1₂) + Ni₃V(DO₂₂) phases, was prepared based on the pseudo-ternary system Ni₃Al–Ni₃Ti–Ni₃V. The high-temperature tensile deformation, fracture behavior and tensile creep were investigated using single crystalline material. The alloy with such a novel microstructure shows extremely high yield and tensile strength with good temperature retention, when compared not only with conventional Ni-based superalloys but also with polycrystalline materials reported previously. Over a broad temperature range fracture occurred along octahedral plane in the major component L1₂ phase, accompanied with high tensile elongation and ductile fracture mode. The tensile creep test conducted at 1173 K and 1223 K showed the presence of threshold stress, and also extremely low creep rate and long creep rupture time when compared with conventional Ni-based superalloys. The obtained results are promising for the development of a new-type of high-temperature structural material.     

Shearing of γ′ precipitates by a〈1 1 2〉 dislocation ribbons in Ni-base superalloys: A phase field approach

The phase field model of dislocations has been used to study the propagation of dislocation ribbons with an overall Burgers vector of a〈1 1 2〉 through a simulated Ni-base superalloy. The driving force for dislocation dissociation reactions and formation of planar faults is incorporated into the free energy functional using periodic functions specially fitted to ab initio γ-surface data. The model shows that the mechanism of cutting of the γ′ precipitates by these ribbons exhibits significant dependence on stress magnitude, orientation and precipitate shape. In the case of mixed screw–edge ribbons a change of shearing mode is observed, from stacking fault shear to anti-phase boundary shear, when the applied stress approaches the yield of the material. This transition is absent in pure edge ribbons.     

Creep- and coarsening properties of Al–0.06 at.% Sc–0.06 at.% Ti at 300–450 °C

Upon aging at 300–450 °C, nanosize, coherent Al₃(Sc_1−xTi_x) precipitates are formed in pure aluminum micro-alloyed with 0.06 at.% Sc and 0.06 at.% Ti. The outstanding coarsening resistance of these precipitates at these elevated temperatures (61–77% of the melting temperature of aluminum) is explained by the significantly smaller diffusivity of Ti in Al when compared to that of Sc in Al. Furthermore, this coarse-grained alloy exhibits good compressive creep resistance for a castable, heat-treatable aluminum alloy: the creep threshold stress varies from 17 MPa at 300 °C to 7 MPa at 425 °C, as expected if the climb bypass by dislocations of the mismatching precipitates is hindered by their elastic stress fields.     

Microstructure,martensitic transformation and anomalies in c′-softening in Co–Ni–Al ferromagnetic shape memory alloys

The morphology, microstructure and elastic softening in single crystals of Co–Ni–Al ferromagnetic shape memory alloy were studied to clarify the conditions for martenstic transformation in this alloy. We used two-phase (β matrix + γ particles) samples with different heat treatments, as-cast and annealed at temperatures from 1523 to 1623 K, and a sample of pure β (B2) phase. A complete set of elastic coefficients at room temperature and the temperature dependence of the softest shear coefficient (c′) of the Co₃₈Ni₃₃Al₂₉ austenite was measured by a combination of pulse echo and resonant ultrasound spectroscopy in the range 208–398 K. All examined materials exhibit anomalous c′-softening for the whole temperature range except the interval 258– 328 K, in which a change in the slope appears. However, only annealed samples transformed to martensite. The change in the slope is ascribed to (i) magnetoelastic softening with the absence of a sharp Curie point; (ii) structural stiffening that prevents the martensitic transition in both the as-cast and single-phase alloys. No signature of the premartensite phenomenon was found.     

Banded-like morphology and martensitic transformation of dual-phase Ni–Mn–In magnetic shape memory alloy with enhanced ductility

Two of the current challenges facing producers of Ni–Mn–In alloys are the achievement of small hysteresis and good ductility. Here, we present a dual-phase (β-Ni_51.8Mn_31.4In_16.8 and γ-Ni_62.4Mn_32.5In_5.1) Ni₅₂Mn₃₂In₁₆ alloy prepared by the zone melting liquid metal cooling directional solidification method, which simultaneously shows small hysteresis (ΔT < 10 K) and good ductility (6.6%). In addition, and more importantly, an inter-martensitic transition with a large magnetization jump occurs in this alloy. This is expected to further broaden the working temperature range of actuators and sensors that use this magnetic shape memory alloy. The sequence of the martensitic transformation can be shown by in situ X-ray diffraction to be austenite → 10M → 14M. Additionally, the second (γ) phase dramatically enhances the entropy change of these structural transformations and shifts them to higher temperatures. During the directional solidification, a novel banded-like microstructure, consisting of two layers, one of the β single phase and the other of the two phases coupled, forms at the low growth rate. A qualitative model is presented to explain the experimental observation, taking into account both the competitive nucleation and the growth of the phases. Experimental and theoretical analysis in the present work shows a linear relationship between the maximum spacing of the β single phase layer and the growth rate.     

Phase formation and thermal stability in Cu–Zr–Ti(Al) metallic glasses

In the present study we investigate the phase formation and the thermal stability of Cu₅₀Zr_50 ? xTi_x (0 ≤ x ≤ 10) and (Cu_0.5Zr_0.5)_100 ? xAl_x glass-forming alloys. Parameters indicating the glass-forming ability (GFA) are calculated from isochronal and isothermal calorimetric experiments. A high Ti content in the Cu–Zr–Ti alloys causes the precipitation of a metastable ternary Laves phase (C15), which does not form in Cu–Zr–Al. Accompanied with it is a significant drop in the activation energy of crystallization. Also the supercooled liquid region (ΔT_x = T_x ? T_g), the reduced glass transition temperature (T_rg = T_g/T_liq), and the γ parameter (γ = T_x/(T_g + T_liq)) (T_x: crystallization temperature, T_g: glass transition temperature and T_liq: liquidus temperature) are sensitive to the change in the crystallization sequence. The fragility values calculated are believed to overestimate the GFA of the investigated alloys. Careful selection of the alloy composition enables the targeted precipitation of different crystalline phases.     

Investigations on the growth kinetics of Laves phase precipitates in 12% Cr creep-resistant steels: Experimental and DICTRA calculations

The growth kinetics of Laves phase precipitates (type Fe₂W) in the early stage of creep (650 °C for 10,000 h) in two 12% Cr ferrite–martensitic steels has been investigated. In one alloy the Laves phase formed on tempering, while in the second alloy the Laves phase precipitated during creep. Kinetic simulations were performed using the software DICTRA. The particle size of the Laves phase was measured on transmission electron microscopy samples. The equilibrium phase fraction of the Laves phase was reached in the first thousand hours. Simulations of particle growth showed good agreement with the experimental results. Competitive growth between M₂₃C₆ and the Laves phase showed that M₂₃C₆ carbides reached their equilibrium after 12 days, whereas the Laves phase reached equilibrium after 3 months. Simulations of the influence of the interfacial energy and addition of Co, Cu and Si on Laves phase precipitation are presented.     

Effects of rhenium addition on the temporal evolution of the nanostructure and chemistry of a model Ni–Cr–Al superalloy. I: Experimental observations

The temporal evolution of the nanostructure and chemistry of a model Ni–8.5 at.% Cr–10 at.% Al alloy, with the addition of 2 at.% Re, aged at 1073 K from 0.25 to 264 h, was studied. Transmission electron microscopy and atom-probe tomography were used to measure the number density and mean radius of the γ′ (L1₂ structure)-precipitates and the chemistry of the γ′-precipitates and the γ (face-centered cubic)-matrix, including the partitioning behavior of all alloying elements between the γ- and γ′-phases and the segregation behavior at γ/γ′ interfaces. The precipitates remained spheroidal for an aging time of up to 264 h and, unlike commercial nickel-based superalloys containing Re, there was not confined (nonmonotonic) Re segregation at the γ/γ′ interfaces.     

Solidification behavior of γ′-Ni3Al-containing alloys in the Ni–Al–O system

The chemical activities of Al and Ni in γ′-Ni₃Al-containing alloys were measured using the multi-cell Knudsen effusion-cell mass spectrometry technique, over the composition range 8–32 at.% Al and temperature range T = 1400 to 1750 K. From these measurements a better understanding of the equilibrium solidification behavior of γ′-Ni₃Al-containing alloys in the Ni–Al–O system was established. Specifically, these measurements revealed that (i) γ′-Ni₃Al forms via the peritectiod reaction, γ + β (+Al₂O₃) = γ′ (+Al₂O₃), at 1633 ± 1 K; (ii) the {γ + β + Al₂O₃} phase field is stable over the temperature range 1633–1640 K; and (iii) equilibrium solidification occurs by the eutectic reaction, L (+Al₂O₃) = γ + β (+Al₂O₃), at 1640 ± 1 K and a liquid composition of 24.8 ± 0.2 at.% Al (at an unknown oxygen content). When projected onto the Ni–Al binary, this behavior is inconsistent with the current Ni–Al phase diagram and a new diagram is proposed. This new Ni–Al phase diagram explains a number of unusual steady-state solidification structures reported previously and provides a much simpler reaction scheme in the vicinity of the γ′-Ni₃Al phase field.     

Phase equilibria in the Ni-rich portion of the Ni–Ga binary system

The phase equilibria in the composition range from 0 to 60 at% Ga of the Ni–Ga system were determined by electron probe microanalysis (EPMA) using diffusion couples, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). It was found that while the phase equilibria between the α′ (L1₂: Ni₃Ga) and α (Ni-solid solution) or β (B2: NiGa) phases are basically in agreement with the diagram evaluated by Lee and Nash, those between γ (B8₁: Ni₁₃Ga₇), δ (Cmmm: Ni₅Ga₃) and ɛ (C2/m: Ni₁₃Ga₉) are topologically different from that diagram. Three eutectoid reactions (γ → δ + ɛ, β → γ + ɛ, β → α′ + γ) and one peritectoid reaction (α′ + γ → δ) were confirmed and the temperatures and concentrations of those invariant reactions were determined.