Transitions between stress-induced martensites in Cu Al Ni alloys

Stress-induced martensitic transformations have been studied in β₁ Cu Al Ni single crystals at temperatures aboveM _s . Close toM _s γ′ martensite is formed, well aboveM _s β ₁ ′ martensite forms, whilst in an intermediate temperature range β₁′ martensite initially forms and then transforms to γ′ on continued stressing and particularly on unloading, γ′ martensite is also formed when the stress-induced β₁′ is cooled below a critical temperature. The γ′ martensite has a (101) twinned structure. The morphological and crystallographic aspects of the γ₁′→ γ′ transition are discussed in detail. The two twin variants have different habit planes with respect to the β₁′ phase, one being (201)γ′ and the other (001)γ′. A thermodynamic argument is presented to explain the γ₁′→ γ′ transition, taking into account the relative stabilities of the β₁′ and γ′ phases with respect to the β₁, and the relative value for the critical driving force to nucleate the stress-induced β₁′ and γ′ structures from the β₁ phase Formerly Post Doctoral Fellow, Department of Metallurgy, University of British Columbia, Vancouver, Canada     

Metastable phases in the Ti-V system: Part I. Neutron diffraction study and assessment of structural properties

This article presents the results of a neutron diffraction study of a series of quenched Ti-V alloys and an assessment of the composition dependence of the structural properties in the Ti-V system. Upon quenching to room temperature and atmospheric pressure, three metastable phases occur, viz., the hcp (α′) phase formed by a martensitic transformation, the omega (Ω) phase formed by a displacive transformation involving the collapse of the (111) planes of the bcc structure, and the untransformed bcc (β) phase. The lattice parameters (LPs) of the α′, β, and Ω phases are determined as functions of the V content in the composition range 3 ≤ at. pct V ≤ 70. This information is combined with a detailed analysis of the available experimental data on the α′, β, and Ω phases in pure Ti and Ti-V alloys and the β phase of V. New estimates for the LPs of β and Ω Ti and expressions describing the composition dependence of the LPs are presented. Using the assessed values, various open questions are discussed, i.e., the composition range where the hexagonal to trigonal symmetry change is observed in the Ω phase, the applicability of an approximation involved in the plane collapse model for the β → Ω transformation, and the extent to which the so-called Jamieson correlation for interatomic distances in the Ω phase holds for Ti.     

Microstructure and its development in Cu-Al-Ni alloys

The microstructure of as-cast Cu-AI-Ni alloys, based on copper containing 9 to 10 wt pct Al and up to 5 wt pct Ni, has been examined. The development of the microstructure on continuous cooling has also been investigated. For alloys with 9.2 to 9.3 wt pct Al, and less than 1 wt pct Ni, the as-cast microstructure consists of proeutectoid α solid solution, α + γ₂ eutectoid, and martensitic β. If the nickel content is more than 2.5 wt pct, the α + γ₂ eutectoid is replaced by α + β ₂ ^′ eutectoid, and no martensitic β is observed in the as-cast alloys. The morphologies of the β ₂ ^′ and γ₂ eutectoid phases are similar; both have the Kurdjumov-Sachs (K-S) orientation relationship with the a phase. Two eutectoid reactions, involving β to α + γ₂ and β to α + β′₂, have been observed in an alloy containing 9.7 wt pct Al and 2.7 wt pct Ni. When both eutectoid reactions occur, the Nishiyama-Wassermann (N-W) orientation relationship exists between γ₂ or β ₂ ^′ and the α phase. During continuous cooling, proeutectoid α solid solution is the first phase to precipitate from the high-temperature β phase. The β to α + β ₂ ^′ eutectoid reaction starts at higher temperatures than the β to α + γ₂ reaction. Tempering of the as-cast alloys results in the elimination of the martensitic β. Y.S. SUN formerly Research Associate with the Manchester Materials Science Centre.     

Partition of alloying elements between γ (A1), γ′ (L12), and β (B2) phases in Ni-Al base systems

Phase equilibria between γ (Al), γ′ (Ll₂), and β (B2) phases in the Ni-rich portions of the Ni-Al-X ternary systems were investigated over a temperature range of 800 °C to 1300 °C. The tie lines and phase boundaries were accurately determined by the diffusion couple technique. It was established that Co, Cu, Mn, Fe, and Cr concentrated more into the γ phase than into the γ′ phase, while Ta, Nb, Ti, V, and Si mostly partitioned to the γ′ phase. The partition coefficients for alloying elements between γ and γ′ phases varied as a function of temperature for most of the elements and also as a function of concentration for some of the elements, such as Mo, W, and V. In the equilibrium between γ′ and β phases, Mn, Fe, Co, and Cu partitioned to the β phase rather than to the γ′ phase, whereas Nb, Mo, Ta, Ti, W, V, Cu, and Si concentrated into the γ′ phase. The partition of alloying elements in the metastable equilibrium between γ and β phases, in the Ni-Al binary system, was estimated from the data on γ/γ′ and γ′/β equilibria. Based on these data, the relative stabilizing effects of alloying elements on γ, γ′, and β phases are also discussed.     

Interdiffusion structures and paths for multiphase Fe-Ni-Al diffusion couples at 1000 °C

Diffusion studies were carried out in the Fe-Ni-Al system at 1000 °C using solid-solid diffusion couples assembled with β (B₂), γ (fcc) single phase, and (β + γ) two-phase alloys. The diffusion couples were encapsulated in quartz tubes under vacuum and annealed for 48 hours. The diffusion structures were examined by optical and scanning electron microscopy. For all β vs (β + γ) couples, growth of the β phase was observed as the (β + γ) two-phase region recessed with the dissolution of the γ phase. For multiphase couples assembled with two (β + γ) terminal alloys, demixing of the (β + γ) two-phase alloys occurred with the formation of single-phase β and γ layers. The development of an interphase boundary between the (β + β′) two-phase region and the γ phase is reported for the first time for a Fe-Ni-Al diffusion couple assembled with single-phase, β, and γ terminal alloys. Various diffusion structures for the couples were related to their diffusion paths constructed from concentration profiles determined by electron probe microanalysis. Interdiffusion fluxes of individual components were determined directly from the experimental concentration profiles and examined in light of diffusional interactions and the development of zero-flux planes and flux reversals. In addition, the boundaries for the miscibility gap between the ordered β and disordered β′ phases of the Fe-Ni-Al system at 1000 °C were determined with the aid of diffusion couples that developed β and β′ phases in the diffusion zone.     

Microstructural evolution of the nickel platinum-aluminide bond coat on electron-beam physical-vapor deposition thermal-barrier coatings during high-temperature service

The microstructural evolution of a (Ni,Pt)-aluminide bond coat underneath the ZrO₂-based thermal-barrier coating (TBC) topcoat system on a René N5 Ni-based superalloy turbine blade during prolonged high-temperature service has been characterized using transmission electron microscopy (TEM). The as-deposited bond coat has a spatially varying microstructure, which consists of an outer layer of single-phase β-(Ni,Pt)Al, a middle layer of a β-(Ni,Pt)Al matrix containing a high number density of μ-phase precipitates, and an inner layer containing a γ/γ′ matrix and numerous μ- and σ-phase precipitates. During service, microstructural changes in the hotter sections of the blade are more extensive than those in the cooler parts, as expected. As a result of interdiffusion, the inner layer grows into the γ/γ′ substrate, with the formation of some M₂₃C₆ precipitates, and the β matrix in the middle layer is transformed into a two-phase mixture of β and γ′. Corresponding changes occur in the morphologies and volume fractions of the various precipitate phases present in the bond coat. The single-phase β material in the outer layer retains its basic structure, except that the compositional changes due to diffusion between the bond coat and turbine blade cause a martensitic transformation to occur in the hottest sections during the final cooling of the blade. The distribution of various elements in the different layers has also been analyzed, as has growth of the thermally grown oxide (TGO) at the bond coat/TBC interface.     

The thermodynamics of stress-induced martensites in Cu Al Ni alloys

Stress-induced martensitic transformations have been studied in Β₁ Cu Al Ni single crystals in which two martensite crystal structures can form, Β _i ^′ and γ′. By straining specimens at one temperature and releasing the strain at either the same temperature or a different temperature, stresses corresponding to the transitions Β₁ ⇌ Β _i ^′ ,Β ₁ ⇌ γ′,Β _i ^′ ⇌ γ′ could all be measured. This enabled a quantitative stress-temperature diagram to be drawn, giving the stability ranges of the Β₁,Β _i ^′ and γ′ phases. The slope of the stress-temperature lines separating the different phases enabled the value of the entropy changes for the transformations to be calculated. This was very small for theΒ _i ^′ → γ′ transformation (0.08 J/mole K) and much larger for the Β₁ →Β _i ^′ and Β₁ → γ′ transformations (-1.21 and -1.4 J/mole K, respectively). The hysteresis between the forward and reverse transformations enabled evaluation of the critical free energy for transformation. This was small for the Β₁ → Β _i ^′ transformation (-2.9 J/mole), and large for the Β₁ → γ′ and Β _i ^′ → γ′ transformations (-28 and -29 J/mole respectively). Formerly Post Doctoral Fellow, Department of Metallurgy, University of British Columbia     

The morphology and substructure of martensite in maraging steels

Thin foil transmission electron microscopy, X-ray diffraction and dilatometric techniques have been used to study the martensitic γ → α transformation in three steels with nominal contents of 8 pct nickel and 0.2 pct beryllium and chromium contents of 12, 14 and 16 pct. In each case the martensite formed as laths with a habit plane close to {225}_γ. With increasing chromium content and increasing cooling rate greater numbers of the laths were observed to be internally twinned. Detailed analysis of the martensitic transformation suggested that the internally twinned laths are formed by a sequence of γ→ ε or faulted γ→ ά. The orientation relationships between the three phases γ, ε and α, determined from selected area diffraction analysis, corresponded to Kurdjumov-Sachs.     

Interdiffusion in Ni-Rich,Ni-Cr-Al alloys at 1100 and 1200 °C: Part I. Diffusion paths and microstructures

Interdiffusion in Ni-rich, Ni-Cr-Al diffusion couples was studied after annealing at 1100 and 1200 °C. Recession of γ′ (Ni₃Al structure), β (NiAl structure), or α (bcc) phases was also measured. Aluminum and chromium concentration profiles were measured in the γ (fcc) phase for most of the diffusion couples. The amount and location of Kirkendall porosity suggests that Al diffuses more rapidly than Cr which diffuses more rapidly than Ni in the γ phase of Ni-Cr-Al alloys. The location of maxima and minima in the concentration profiles of several of the diffusion couples indicates that both cross-term diffusion coefficients for Cr and Al are positive and that D_CrAl has a greater effect on the diffusion of Cr than does D_A1Cr on the diffusion of Al. The γ/γ + β phase boundary has also been determined for 1200 °C through the use of numerous γ/γ+ β diffusion couples.     

Driving force for γ→ε martensitic transformation and stacking fault energy of γ in Fe-Mn binary system

A regular solution model for the difference of the chemical free energy between γ and ε phases during γ→ε martensitic transformation in the Fe-Mn binary system has been reexamined and partly modified based on many articles concerning the M _s and A _s temperatures of Fe-Mn alloys. Using the regular solution model, the measured M _s temperatures, and a thermodynamic model for the stacking fault energy (SFE) of austenite (γ), the driving force for γ→ε martensitic transformation, and the SFE of γ have been calculated. The driving force for γ→ε martensitic transformation increases linearly from − 68 to − 120 J/mole with increasing Mn content from 16 to 24 wt pct. The SFE of γ decreases to approximately 13 at. pct Mn and then increases with increasing Mn content, which is in better agreement with Schumann’s result rather than Volosevich et al.’s result.     

Observations and analysis of the influence of phase transformations on the instability of the thermally grown oxide in a thermal barrier system

Observations and measurements have been performed on a thermal barrier system comprising a Ptaluminide bond coat and a thermal barrier coating deposited by electron beam evaporation. Past research has highlighted a displacement instability in the thermally grown oxide (TGO), as it affects the failure mechanism in the thermal barrier coating (TBC). Phase transformations in the bond coat have also been identified, with a proposed role in the TGO instability. The present study assesses this influence by characterizing the transformations as well as their spatial correlation with the instability sites. Both the isothermal transformation from β→γ′ and the martensite transformation in the β have been addressed. Toward the end of life, the instabilities are preferentially located in the β phase, between neighboring domains of γ′. After cycling, the composition of the β grains is spatially uniform. Within the γ′, there are Ni and Al composition gradients in narrow layers near the interfaces with the β phase and the TGO. An evaluation suggests that the primary influence of transformation on the cyclic displacement of the TGO is to create a local misfit between the growing γ′ domains and the volume strain accompanying the martensite transformation in the intervening β phase, upon cooling and reheating.     

Structure of phases in the δ-AI2O3 fiber studied by convergent beam electron diffraction

The phases in the δ-Al₂O₃ fibers were investigated using the methods of transmission electron microscopy (TEM): convergent beam electron diffraction (CBED) and high-resolution electron microscopy (HREM). A phaseγ′-Al₂O₃ discovered previously by Vewerly in oxide layers with an fcc structure was found and new atomic positions are proposed. A new structure ofδ-Al₂O₃ was also observed. It has aPmma space group and lattice parameters ofa _δ = 2a _γ′,b _δ = l.5a _γ′, andc _δ ≈a _γ′ The correlation of the observed A1₂O₃ lattices to the spinel lattice is discussed and translation of atom positions during theγ′ →γ →δ transformation is studied. All anions must change their positions by a small amount; one-third of the cation positions inγ′ and more than 90 pct of cation positions inδ experience a large translation during that transformation. This implies that for theγ′ it→γ} →δ transformation, the positions of cations in both lattices are important. The results are discussed in relation to the fiber-matrix interaction under spinel formation during thermal loading ofδ-Al₂O₃-fiber-reinforced aluminum piston alloys.     

Deformation and fracture behavior of a directionally solidified β/γ′ Ni-30 At. pct Al alloy

The effect of a ductile γ′-Ni₃Al phase on the room-temperature ductility, temperature-dependent yield strength, and creep resistance of β-NiAl was investigated. Room-temperature tensile ductility of up to 9 pct was observed in directionally solidified β/γ′ Ni-30 at. pct Al alloys, whereas the ductility of directionally solidified (DS), single-phase [001] β-NiAl was negligible. The enhancement in ductility was attributed to a combination of slip transfer from the ductile γ′ to the brittle β phase and extrinsic toughening mechanisms such as crack blunting, deflection, and bridging. As in single-phase Ni₃Al, the temperature-dependent yield strength of these two-phase alloys increased with temperature with a peak at approximately 850 K. The creep strength of the β/γ′ alloys in the temperature range 1000 to 1200 K was found to be comparable to that of monolithic β-NiAl. A creep strengthening phase needs to be incorporated in the β/γ′ microstructure to enhance the elevated temperature mechanical properties.     

Lattice misfits in four binary Ni-Base γ/γ1 alloys at ambient and elevated temperatures

High-temperature X-ray diffractometry was used to determine thein situlattice parameters,a _γ anda _γ′, and lattice misfits, δ = (a _γ′, -a _γ)/a _γ, of the matrix (γ) and dispersed γ′-type (Ni₃X) phases in polycrystalline binary Ni-Al, Ni-Ga, Ni-Ge, and Ni-Si alloys as functions of temperature, up to about 680 °C. Concentrated alloys containing large volume fractions of theγ′ phase (∼0.40 to 0.50) were aged at 700 °C to produce large, elastically unconstrained precipitates. The room-temperature misfits are 0.00474 (Ni-Al), 0.01005 (Ni-Ga), 0.00626 (Ni-Ge), and -0.00226 (Ni-Si), with an estimated error of ± 4 pct. The absolute values of the lattice constants of theγ andγ′ phases, at compositions corresponding to thermodynamic equilibrium at about 700 °C, are in excellent agreement with data from the literature, with the exception of Ni₃Ga, the lattice constant of which is much larger than expected. In Ni-Ge alloys, δ decreases to 0.00612 at 679 °C, and in Ni-Ga alloys, the decrease is to 0.0097. In Ni-Si and Ni-Al alloys, δ exhibits a stronger temperature dependence, changing to-0.00285 at 683 °C (Ni-Si) and to 0.00424 at 680 °C (Ni-Al). Since the times required to complete the high-temperature X-ray diffraction (XRD) scans were relatively short (2.5 hours at most), we believe that the changes in δ observed are attributable to differences between the thermal expansion coefficients of theγ andγ′ phases, because the compositions of the phases in question reflect the equilibrium compositions at 700 δC. Empirical equations are presented that accurately describe the temperature dependences ofa _γ,a _γ′, and δ over the range of temperatures of this investigation.     

<Emphasis Type="Italic">In-Situ</Emphasis> Synchrotron Characterization of Transformation Sequences in TiNi-Based Shape Memory Alloys during Thermal Cycling

In-situ synchrotron radiation has been used to provide direct analysis of the transformation sequences in TiNi-based shape memory alloys during thermal cycling. The high resolution, narrow peak width Debye–Scherrer diffraction spectra enabled positive identification and quantification of the phase transformation sequences, which is not possible through normal laboratory studies. The results facilitate a clearer understanding of the development and influence of intermediate phases such as R or B19 on sequential martensitic transformations. Ti_50.2Ni_49.8 transformed predominately via a single-step B2 ↔ B19′ transformation, although evidence of the R phase was found during cooling in every cycle. The martensitic start temperature was depressed by ~0.6 °C per cycle, while the R-phase start temperature was found to be unaffected. Ti₅₀Ni₄₁Cu₉ transformed through a two-step B2 ↔ B19 ↔ B19′ sequence, with the B2 → B19 transformation reaching completion prior to the formation of any B19′. The transformation temperatures of Ti₅₀Ni₄₁Cu₉ were found to be insensitive to thermal cycling, remaining constant over the studied cycle range.     

A theoretical model for the flow behavior of commercial dual-phase steels containing metastable retained austenite: Part II. calculation of flow curves

The role of metastable retained austenite(γ _R), its volume fraction, and mechanical stability on the flow characteristics of a dual phase steel containing 20 vol pct of ‘as quenched’ martensite in a ferrite matrix has been examined in this paper employing the flow curve expressions derived in Part I of this paper. It has been found that for a given volume fraction ofγ _R, its mechanical stability plays a crucial role in enhancing the ductility. Whereas highly stableγ _R does not contribute either to strength or ductility of the steel, highly unstableγ _R which causes an increase in the strength is detrimental to ductility. Aγ _R which is moderately stable and undergoesγ _R → α′ transformation over a larger strain range is beneficial to enhanced ductility. Increasing amounts of moderately stableγ _R significantly increase both the strength and the ductility of dual-phase steels through a sustained work-hardening due toγ _R → α′ transformation. Load transfer which is determined by a parameterq has a significant contribution to work-hardening. A value of ∣|q∣|= 4500 MPa has been found to partition realistically the stress and strain in these steels.     

Martensitic phase transformations in IMI 550 (Ti-4Al-4Mo-2Sn-0.5 Si)

The influence of solution-treatment temperature on the martensitic phase transformations observed in IMI 550 (Ti-4Al-4Mo-2Sn-0.5Si) has been investigated. When solution treatment is conducted at temperatures above 1233 K, a hexagonal martensite (α′) is formed on rapid cooling. However solution treatment at temperatures between 1233 and 1123 K results in the formation of an orthorhombic martensite (α″) on rapid cooling. Finally, below 1123 K, the β phase is stable—no martensitic transformation occurs on rapid cooling. This transition from α′ → α _primary + (α′ + β _retained) → α _primary + (α″ + β _retained) → α _primary + β _metastable + ω, with decreasing solution-treatment temperature, is shown to be a result of alloy partitioning during solution treatment. Crystallographic analysis indicates that the transition in the martensite crystal structure with decreasing solution-treatment temperature is related to chemical short-range ordering (CSRO) in the high-temperature β phase.     

Diffusion studies in the β (B2), β′ (bcc), and γ (fcc) Fe-Ni-Al alloys at 1000 °C

Diffusion studies were carried out in the Fe-Ni-Al system at 1000 °C with solid-solid diffusion couples assembled with β (B₂), β′ (bcc), and γ (fcc) single-phase alloys for the development of diffusion structures, diffusion paths, and for the determination of interdiffusion and intrinsic diffusion coefficients. The diffusion structures were examined by optical and scanning electron microscopy, and the concentration profiles were determined by electron microprobe analysis. Diffusion couples included several series of β vs γ and β′ vs γ diffusion couples characterized by a common terminal alloy bonded to several terminal alloys with varying compositions. The development of planar and nonplanar interfaces, as well as two-phase layers, as observed in various couples, were related to the diffusion paths. The interdiffusion fluxes of individual components were calculated directly from the experimental concentration profiles, and the diffusional interactions among components were examined in the light of zero-flux planes (ZFPs) and flux reversals, which were identified in several couples. Ternary interdiffusion coefficients ( (i, j = Al, Ni)), with Fe considered as the dependent concentration variable, were evaluated at composition points of the intersection of diffusion paths of single-phase couples and of multiphase couples that developed planar interfaces. The interdiffusion coefficients were the largest in magnitude for the β′ alloys, especially near the β/β′ miscibility gap, and decreased for the β and γ alloys. In the β and γ phases, the main interdiffusion coefficient for Al was larger than those for Ni and Fe. Also, Fe interdiffused faster than Ni in the Fe-rich β and β′ phases. The cross-interdiffusion coefficients ( and ) were negative in all three phases. In general, the coefficients were larger in magnitude than the coefficients; however, the magnitude of was greater than that of near the β/(β + γ) phase boundary on the ternary isotherm. In the β phase, the magnitude of (i, j=Al, Ni) coefficients increased over 1 to 2 orders of magnitude with a decrease in the Al concentration and increase in the Fe/Ni concentration ratio. Interdiffusion coefficients, extrapolated from the ternary coefficients for binary alloys, were consistent with those in literature. Intrinsic diffusion coefficients were also determined at selected compositions. In addition, tracer diffusion coefficients were estimated for the binary Fe-Al and Ni-Al alloys at selected compositions, from an extrapolation of ternary interdiffusion coefficients.     

The vanadium-platinum constitution diagram

The system V-Pt was investigated over the entire composition range by metallography, X-ray diffraction and electron microprobe studies. There are at least four equilibrium intermediate phases in this system and they are stable to progressively higher temperatures with increasing vanadium concentration. The phases which have been observed are: γ^′, cubic, Cu₃Au type; θ, tetragonal, TiAl₃ type; δ, orthorhombic, MoPt₂ type; ζ, orthorhombic, AuCd type; and β, cubic, Cr₃Si type (A15). The gg^′ phase is possibly metastable. A very stable ribbon-like growth of ζ phase in the fcc platinum terminal solid solution has been observed in alloys containing about 43 at. pct V. The platinum terminal solid solution forms a congruent melting maximum at about 1805°C. A eutectic reaction occurs at 1720° ± 10°C and a peritectic reaction is indicated at 1800° ± 10°C. Vanadium is soluble in the fcc platinum terminal solid solution up to about 57 at. pct at 1720°C. Platinum dissolves only to the extent of about 12 at. pct at 1800°C in bcc α-V.