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Alloying NiTi shape memory alloys with sufficient Pt and Pd at the expense of Ni has been shown to increase transformation temperatures well above those possible with the binary composition, enabling consideration of a new class of high-temperature mechanical sensors and actuators. To achieve shape memory behavior at temperatures greater than 200 °C, previous studies of NiTiPt and NiTiPd compositions have focused primarily on alloys with greater than 16 at.% Pt and 25 at.% Pd. While generally not the focus, none of these previous studies demonstrated superelastic behavior at high temperatures. In an effort to identify alloys that transform to austenite at approximately 200 °C and exhibit superelastic behavior with recoverable strains greater than 2%, a series of Ti-rich NiTiPt ternary alloys with 15.5–16.5 at.% Pt, and Ti-rich NiTiPd ternary alloys with 25–26 at.% Pd have been targeted. The polycrystalline alloys were processed via arc melting followed by homogenization heat treatment. Thermomechanical properties were measured using electro-discharge machined tension test coupons and a miniature load frame equipped with a clamshell furnace. Ultimately, superelasticity in uniaxial tension with clear plateau regions was demonstrated and characterized in these alloys at temperatures between 219 °C and 270 °C.

Machine learning was utilized to efficiently boost the development of soft magnetic materials. The design process includes building a database composed of published experimental results, applying machine learning methods on the database, identifying the trends of magnetic properties in soft magnetic materials, and accelerating the design of next-generation soft magnetic nanocrystalline materials through the use of numerical optimization. Machine learning regression models were trained to predict magnetic saturation ($B_S$), coercivity ($H_C$) and magnetostriction ($\lambda$), with a stochastic optimization framework being used to further optimize the corresponding magnetic properties. To verify the feasibility of the machine learning model, several optimized soft magnetic materials -- specified in terms of compositions and thermomechanical treatments -- have been predicted and then prepared and tested, showing good agreement between predictions and experiments, proving the reliability of the designed model. Two rounds of optimization-testing iterations were conducted to search for better properties.

Nickel-rich (54–56 at.% Ni) NiTi-based alloys have gained increased attention for their high hardness, corrosion resistance, strength, and wear resistance, leading to their development for high-performance bearings and other wear applications. An investigation of a broader compositional range of NiTiHf alloys, in terms of Ni and Hf content, is presented in this study. Their Vickers micro-hardness, 3 ball-on-rod rolling contact fatigue, and compression performances are benchmarked against early compositions identified for bearing applications, e.g., Ni55Ti45 and Ni54Ti45Hf1. The results show that by varying heat treatments and alloy composition, certain NiTiHf alloys can exhibit long life (~ 107 cycles) at 10–20% greater contact stress levels (up to 2.2–2.4 GPa), together with up to 20% greater hardness (up to 770 HV) and 30% larger compressive yield strengths (up to 3.4 GPa) than the original bearing compositions. These improvements are attributed to the ability to develop alloys with high-volume fractions of fine precipitate phases. Interestingly, a variety of combinations of different precipitate strengthening phases, depending on alloy composition and heat treatment, were able to achieve improvements relative to Ni55Ti45 and Ni54Ti45Hf1, demonstrating the versatility of the NiTiHf system.

The effects of a combined 1.0 at.% W and 1.0 at.% Re addition to a model Ni-10.0Al-8.5Cr at.% superalloy aged at 1073 K (800 °C) for aging times up to 256 h are investigated using atom-probe tomography (APT) and Vickers microhardness measurements. The nanoscale properties, including volume fraction, mean-volume equivalent-radius and number density of the γ′(L12)-precipitates, the chemical compositions of the γ(f.c.c.)-matrix and γ′(L12)-precipitates, the concentration profiles and partitioning ratios between the two phases, γ(f.c.c.)/γ′(L12), hetero-interfacial concentration widths, and microhardness are measured as function of increasing aging time. Localized excesses of the solvent Ni at the γ(f.c.c.)/γ′(L12) interfaces persist at aging times as long as 256 h. Transient diffusional concentration gradients associated with solute-atoms during diffusion-limited growth exist in either the γ(f.c.c.)-matrix or γ′(L12)-precipitates for the as-quenched state; these gradients disappear after 0.25 h for Al and Cr, and after 1 h for W and Re. Tungsten partitions to the γ′(L12)-precipitates and Re partitions to the γ(f.c.c.)-matrix, respectively, and this partitioning behavior enhances the partitioning of Al to the γ′(L12)-precipitates and Cr to the γ(f.c.c.)-matrix. The partitioning behavior indicates that W and Re evolve temporally more slowly than Al and Cr due to their small diffusivities in Ni. The interfacial concentration widths in the Ni-Al-Cr-W-Re alloy decrease with increasing aging time and increasing mean precipitate-radius. Adding W and Re to the base Ni-10.0Al-8.5Cr at.% alloy increases the γ′(L12)-precipitate volume fraction and the microhardness due to the increased volume-fraction and solid-solution strengthening provided by W and Re.

The temporal evolution of ordered γ′(L12)-precipitates precipitating in a disordered γ(f.c.c.) matrix is studied in extensive detail for a Ni-12.5 Al at.% alloy aged at 823 K (550 °C), for times ranging from 0.08 to 4096 h. Three-dimensional atom-probe tomography (3-D APT) results are compared to monovacancy-mediated lattice-kinetic Monte Carlo (LKMC1) simulations on a rigid lattice, which include monovacancy-solute binding energies through 4th nearest-neighbor distances, for the same mean composition and aging temperature. The temporal evolution of the measured values of the mean radius, 〈 R ( t ) 〉 , number density, aluminum supersaturations, and volume fraction of the γ′(L12)-precipitates are compared to the predictions of a modified version of the Lifshitz-Slyozov diffusion-limited coarsening model due to Calderon, Voorhees et al. The resulting experimental rate constants are used to calculate the Gibbs interfacial free-energy between the γ(f.c.c.)- and γ′(L12)-phases, which enter the model, using data from two thermodynamic databases, and its value is compared to all exiting values. The diffusion coefficient for coarsening is calculated utilizing the same rate-constants and compared to all archival diffusivities, not determined from coarsening experiments, and it is demonstrated to be the inter-diffusivity, D ˜ , of Ni and Al. The monovacancy-mediated LKMC1 simulation results are in good agreement with our 3-D APT data. The compositional interfacial width, for the {100}-interface, between the γ(f.c.c.)- and γ’(L12)-phases, decreases continuously with increasing aging time and 〈 R ( t ) 〉 , both for the 3-D APT results and the monovacancy-mediated LKMC1 simulations, in disagreement with an ansatz intrinsic to the trans-interface diffusion-controlled coarsening model, which assumes the exact opposite trend for binary alloys.

The effects of Cr additions on the morphologies οf γ′(L12 ordered) precipitates are studied in three Ni-Al-Cr alloys utilizing atom-probe tomography (APT) and first-principles calculations. We find that Cr and Al share the same sublattice sites in the L12-structure: Chromium partitions from the L12 structure into the disordered f.c.c. matrix for a driving force of 0.436 eV atom−1. Mixing between the Ni3Al(L12) and Ni3Cr(L12) structures is energetically unfavorable based on first-principles quasi-random structure calculations. Interfacial Gibbs free energies of Ni/Ni3Al(L12), Ni/Ni3Cr(L12), Ni/Ni3Cr(DO22), and Nin(AlyCr1-y)/Ni3(AlxCr1-x)(L12) interfaces are calculated for the {100}, {110}, and {111} planes. The temperature dependencies of the interfacial Gibbs free energies are determined by including phonon vibrational entropies. The equilibrium interfacial Gibbs free energies are determined using concentration profiles as a function of aging time, obtained using APT. At early aging times, the initial values of the interfacial Gibbs free energies are higher with small Cr concentrations in the γ’ (L12)-precipitates. With increasing aging time, the interfacial Gibbs free energies decrease with increasing Cr concentration and achieve equilibrium values after 16-h of aging at 873 K (600 °C) for the three Ni-Al-Cr alloys. From classical nucleation theory, the nucleation of metastable Ni3Cr(L12) is easier than Ni3Al(L12) at 873 K (600 °C). Ni3Cr(DO22) is more difficult to nucleate than Ni3Cr(L12) and Ni3Al(L12) at 873 K (600 °C). The Cr additions to Ni-Al alloys have significant effects on the critical radius and critical net reversible work of nucleation. With increasing Cr concentration, Ni3(Al,Cr)(L12) requires the smallest critical net reversible work to form but has a larger critical size. An embryo of Ni3Cr(L12) only acts as a nucleant for mixed L12 Ni3(AlxCr1-x). The morphology of Ni3(Al,Cr)(L12) precipitates transforms from cuboidal-to-spheroidal with increasing Cr concentration, in agreement with APT observations.

The coarsening kinetics and elemental partitioning behavior of γ’-(L12) precipitates in a γ(f.c.c.)-matrix for a model quaternary Co-8.8Al-8.9W-9.9Ni at.% superalloy are investigated utilizing isothermal aging conditions at 650, 800 and 900 °C. The γ′-precipitate mean radius, number density, and volume fraction, at 800 and 900 °C, were studied using scanning electron microscopy; the calculated temporal exponents associated with coarsening of γ′-precipitates display good agreement with model predictions for quasi-stationary coarsening. An atom probe tomographic (APT) investigation of the aged γ/γ′ microstructure at 650 °C demonstrates that the compositions and volume fractions of both phases vary continuously up to 4096 h. The aged microstructure at 650 °C consists of interconnected nanoscale γ′-precipitates, corroborated utilizing SEM for the 4096 h aged-specimen. The activation energy for coarsening is estimated for the temperature range 650–900 °C to be 283 kJ mol−1, in reasonable agreement with activation energies for diffusion of Al, W, and Ni in Co, suggesting that coarsening of γ′-precipitates is limited by bulk-diffusion. APT measurements of specimens aged for 1024 h at 800 and 900 °C demonstrate that the isothermal aging temperature has a significant effect on the compositions and partitioning behavior of Co, Al, W and Ni between the γ- and γ′-phases. The partitioning ratio of the concentrations between the γ′- and γ-phases is largest for W, decreasing linearly from 5.3 ± 0.1 at 650 °C to 2.1 ± 1.2 at 900 °C, and smallest for Co, decreasing from 0.86 ± 0.01 at 650 °C to 0.73 ± 0.01 at 900 °C.

The temporal evolution of ordered gamma-prime(L12)-precipitates and the compositional trajectories during phase-separation of the gamma(face-centered-cubic(f.c.c.)) and gamma-prime(L12)-phases are studied in a Ni-0.10Al-0.085Cr-0.02Re(mole-fraction) superalloy, utilizing atom-probe tomography, transmission electron microscopy, and the Philippe-Voorhees (PV) coarsening model. As the gamma-prime(L12)-precipitates grow, the excesses of Ni, Cr and Re, and depletion of Al in the gamma(f.c.c.)-matrix develop as a result of diffusional fluxes crossing gamma(f.c.c.)/gamma-prime(L12) heterophase interfaces. The coupling effects on diffusional fluxes was introduced (PV coarsening model) in terms of the diffusion tensor, D, and the second-derivative tensor of the molar Gibbs free energies, G", obtained employing Thermo-Calc and DICTRA calculations. The Gibbs interfacial free energies are (6.9 +- 1.4) mJ/m2 with all terms in D and G", which changes to (18.9 +- 2.1) mJ/m2, (37.7 +- 3.3) mJ/m2, and (-7.5 +- 1.2) mJ/m2 without including the off-diagonal terms in D, G", and both D and G", respectively. The experimental APT compositional trajectories are displayed and compared with the PV model in a partial quaternary phase-diagram, employing a tetrahedron. The compositional trajectories measured by APT exhibit curvilinear behavior in the nucleation and growth regimes, which become vectors, moving simultaneously toward the gamma(f.c.c.) and gamma-prime(L12) conjugate solvus-surfaces, for the quasi-stationary coarsening regime. The compositional trajectories are compared to the PV model with and without the off-diagonal terms in D and G". The directions including the off-diagonal terms in D and G" tensors are consistent with the APT experimental data., Comment: 63 pages, 18 figures, 3tables

Mechanisms of crack propagation in a NiTiHf sample were studied from post-mortem microstructure characterizations about cracks. Transmission electron microscopy (TEM) analysis showed that a crack propagated within a martensite band along 〈011〉 type II twin planes. The crack was observed to switch between different twin planes to avoid precipitates. The crack tip terminated outside of the martensite band, within surrounding austenite. Amorphization of crack edges in both austenite and martensite was also detected, together with Ni enrichment. High-resolution TEM examination of crack tip inside the austenite phase also confirmed the formation of martensite nanocrystals embedded in the amorphous regions.

The temporal evolution of a γ(f.c.c.)/γ’ (L1 2 ) Co-8.8Al-7.3 W superalloy aged at 650 °C (10 min–4096 h) and 750 °C (10 min–256 h) is studied utilizing atom-probe tomography (APT), scanning electron microscopy, and Vickers microhardness testing. The evolution of the phase compositions, γ’ (L1 2 ) volume fraction, and mean precipitate radius, 2-D (t)>, are determined. Coarsening rate constants and temporal exponents are calculated for -D (t)> of the γ’ (L1 2 )-nanoprecipitates. The temporal exponents are found to be generally close to 1/p = 1/3 as required for diffusion-limited coarsening. Tungsten solid-solubility is significantly reduced in the γ(f.c.c.)-matrix at 650 °C (0.54 ± 0.04 at. %) and 750 °C (1.35 ± 0.06 at. %) when compared with aging at 900 °C (5.5 at. %). The value of 2D (t)> of the γ’ (L1 2 )-nanoprecipitates increases with increasing aging time corresponding to an increase in the Vickers microhardness; the peak strength was not, however, achieved for the aging times investigated. The morphology of the γ’ (L1 2 )-nanoprecipitates begins as spheroids but transitions to cuboids at longer aging times, with final the γ’ (L1 2 ) volume fractions for aging at 650 °C and 750 °C being ϕ = 53% and 54%, respectively. The effect of quench-rate (either furnace-cooled, air-cooled, oil quenched, or water quenched) from a supersolvus temperature of 1050 °C on the microstructure of the alloy is also investigated. Slow cooling (furnace and air-cooling) is shown to result in a uniform distribution of nanometer sized γ’ (L1 2 )-nanoprecipitates, unlike Ni-based superalloys in which the γ’ (L1 2 )-nanoprecipitates form in a non-uniform or multimodal distribution.

Metal amorphous nanocomposite (MANC) alloys are an emerging class of soft magnetic materials showing promise for a range of inductive components targeted for higher power density and higher efficiency power conversion applications including inductors, transformers, and rotating electrical machinery. Magnetization reversal mechanisms within these alloys are typically determined by composition optimization as well as controlled annealing treatments to generate a nanocomposite structure composed of nanocrystals embedded in an amorphous precursor. Here we demonstrate the concept of spatially varying the permeability within a given component for optimization of performance by using the strain annealing process. The concept is realized experimentally through the smoothing of the flux profile from the inner to outer core radius achieved by a monotonic variation in tension during the strain annealing process. Great potential exists for an extension of this concept to a wide range of other power magnetic components and more complex spatially varying permeability profiles through advances in strain annealing techniques and controls.

A Ni50.3Ti41.7Hf8 alloy was studied after two-step aging treatments consisting of 300 °C for 12 h followed by 550 °C for different times. An anomalous change in transformation temperatures was observed as the second aging time was increased from 7.5 to 13.5 h. Initially with increased aging time (0.5–7.5 h) at 550 °C, coherency strain fields about H-phase precipitates increased. The corresponding backstress favored martensite formation, hence an increase in transformation temperatures. However, a point was eventually reached where misfit dislocations relaxed those strain fields and the effect was reduced, resulting in a decrease in transformation temperatures.

Transmission electron microscopy and mechanical testing were used to determine the effect of pre-aging (300 °C for 12 h) on microstructure and mechanical behavior of a series of Ni50.3Ti49.7 − xHfx shape memory alloys (x = 6, 8, 8.5, 9 at.%) prior to normal aging at 550 °C for 3.5 h. Pre-aging was found to promote homogenous nucleation of nanosized H-phase precipitates, resulting in improved mechanical stability and strength and 4% recoverable compression strain without permanent deformation. The absence of pre-aging generally resulted in heterogeneous formations of larger H-phase precipitates, primarily clustered along grain boundaries, and correlated with poorer mechanical behavior.

We report the chemical partitioning behavior in a series of melt spun, partially crystallized Co(78−x)Fe2MnxB14Si2Nb4 (x = 0.5, 2.0, 4.0, and 6.0) alloys. Upon annealing at 520 °C anneal for 20 min, nanocrystallites precipitated from the amorphous matrix that have been previously reported to decrease the magnetic permeability with increasing Mn content. Transmission electron microscopy identified the crystallites within the continuous amorphous matrix as a mixture of hexagonal close packed and face centered cubic phases with an average size of 7.0 ± 3.0 nm. Atom probe tomography (APT) revealed an increase in chemical partitioning between the ferromagnetic and glass-forming elements upon annealing with the crystallite density increasing with Mn content. This implied an increase in crystallinity and a reduction of point defects (vacancies) that accompanied changes in Mn content during the chemical partitioning process, where the extent of crystallinity would influence magnetic properties.

Polycrystalline Co-10Ni-(9 – x)Al-(9 – x)W-2xTi at% (x = 0, 1, 2, 3, 4) alloys with γ(f.c.c.) plus γ′(L1 2 ) microstructures are investigated, where the γ′(L1 2 )-formers Al and W are replaced with Ti. Upon aging, the initially cuboidal γ′(L1 2 )-precipitates grow and develop a rounded morphology. After 256 h of aging at 1000 °C, the precipitates in the 6 and 8 at% Ti alloys coalesce and develop an irregular, elongated morphology. After 1000 h of aging, replacement of W and Al with Ti increases both the mean radius, , and volume fraction, ϕ , of the γ′(L1 2 )-phase from = 463 nm and ϕ = 8% for 2 at% Ti to = 722 nm and ϕ = 52% for 8 at% Ti. Composition measurements of the γ(f.c.c.)-matrix and γ′(L1 2 )-precipitates demonstrate that Ti substitutes for W and Al in the γ′(L1 2 )-precipitates, increases the partitioning of W to γ′(L1 2 ), and changes the partitioning behavior of Al from a mild γ′(L1 2 )-former to a mild γ(f.c.c.)-former. The grain boundaries in the aged alloys exhibit W-rich precipitates, most likely μ(Co 7 W 6 )-type, which do not destabilize the γ(f.c.c.) plus γ′(L1 2 ) microstructure within the grains. Four important benefits accrue from replacing W and Al with Ti: (i) the alloys’ mass density decrease; (ii) the γ′(L1 2 )-solvus temperature increases; (iii) the γ′(L1 2 ) volume fraction formed during aging at 1273 K (1000 °C) increases; and (iv) the 0.2% offset flow stress increases.

The Ti-Pt phase diagram was revised in light of new findings in the research related to the fabrication of alloys for high temperature shape memory alloy (HTSMA) application. This study focuses on alloys in the composition range 30–40 at.% Pt. Unfortunately, the Ti-Pt phase diagram is poorly understood in this composition range making the development of HTSMAs difficult. Consequently, alloys in this range were cast, heat treated, and characterized using differential thermal analysis (DTA), scanning electron microscopy (SEM), wavelength dispersive spectroscopy (WDS) and transmission electron microscopy (TEM). It will be shown that the peritectoid (Ti 3 Pt + β −TiPt →Ti 4 Pt 3 ) proposed by Biggs and coworkers exists, but because of sluggish transformation kinetic, the high temperature DTA peaks are due to the transformation of β -TiPt to Ti 4 Pt 3 and vice-versa; this sometimes produces a lamellar morphology when the alloys are cooled slowly from temperatures above 1240 °C. In addition, the alloys frequently contained more than two phases even after equilibration treatments. One of these phases is a new phase of approximate composition Ti 5 Pt 3 , which is believed to be stabilized by oxygen.

Microstructure of NiTiHf shape memory alloys can be engineered to have high strength and operate at high stress levels for a large temperature window. Nanoprecipitation is well-known method to improve the strength of materials but it can be employed to NiTiHf alloys to substantially alter their phase transformation characteristics (martensite morphology, transformation strain, hysteresis and stress). The martensitic transformation of Ni-rich Ni51.2Ti28.8Hf20 was severely suppressed in the solution treated condition (900 °C-3h/water quench) and after aging at low temperatures, while the transformation temperatures were greater than 100 °C after 650 °C-3h aging. Generation of nanosize precipitates (∼20 nm in size) after 3 h aging at 450 °C and 550 °C improved the strength of the material, resulting in a near perfect dimensional stability during isobaric thermal cycling at stress levels of greater than 1500 MPa, with work output of 20–30 J cm−3. Superelastic behavior with 4% recoverable strain was demonstrated at low temperatures (−20 to 40 °C) after aging at 450 °C-3h and at elevated temperatures (120–160 °C) after aging at 550 °C-3h, with stresses reaching 2 GPa without the onset of plastic deformation. A clear relationship between thermal treatments, microstructure, mechanical and shape memory properties will be shown.

Substituting Ni with Au in NiTi leads to dramatic increases in transformation temperatures, meeting one of the requirements for a viable high temperature actuator material. Consequently, four alloys containing between 49 and 51 at.% Ti, a fixed 40 at.% Au, and balance Ni, were prepared and investigated in detail using load-biased thermal cycling (LBTC), scanning electron microscopy (SEM), aberration corrected scanning transmission electron microscopy (STEM), and X-ray energy dispersive spectroscopy (XEDS). LBTC experiments demonstrated work output well above 400 °C, with full recovery up to 100 MPa. The alloys exhibit minimal variation in shape memory properties despite the relatively large composition range from Ti-lean to Ti-rich, in stark contrast to most other NiTi-based systems, which demonstrate extreme compositional sensitivity. Electron beam analysis revealed the presence of two types of secondary phases present in all compositions, which are subsequently characterized. Differences in secondary phase content as a function of alloy composition is shown to have a moderating effect on the transforming matrix composition - an important asset for this alloy system - potentially easing processing requirements and opening up shape memory alloys to new fabrication techniques. Unrecovered strain during cycling at higher loads is analyzed from a theoretical perspective to gain insight into the mechanisms of defect formation responsible for functional fatigue.

The effects of various heat treatments on the microstructure and hardness of new Ni56Ti41Hf3 and Ni56Ti36Hf8 (atomic %) alloys were studied to evaluate the suitability of these materials for tribological applications. A solid-solution strengthening effect due to Hf atoms was observed for the solution annealed (SA) Ni56Ti36Hf8 alloy (716 HV), resulting in a comparable hardness to the Ni56Ti41Hf3 alloy containing 54 vol.% of Ni4Ti3 precipitates (707 HV). In the Ni56Ti41Hf3 alloy, the maximum hardness (752 HV), achieved after aging at 300°C for 12 h, was attributed to dense, semi-coherent precipitation of the Ni4Ti3 phase. Unlike the lenticular morphology usually observed within binary NiTi alloys, a “blocky” Ni4Ti3 morphology formed within Ni56Ti36Hf3 due to a smaller lattice mismatch in the direction normal to the habit plane at the precipitate/matrix interface. The maximum hardness for Ni56Ti36Hf8 (769 HV) was obtained after applying an intermediate aging step (300 °C for 12 h) followed by normal aging (550 °C for 4 h). This two-step aging treatment induces dense nanoscale precipitation of two interspersed precipitate phases, namely H-phase and a new cubic Ni-rich precipitate phase, resulting in the highest hardness exhibited yet by this family of alloys. The composition and structure of this new precipitate phase was characterized using atom probe tomography and transmission electron microscopy techniques to be cubic with a lattice parameter of a = 8.87 A and symmetry belonging to one of the primitive subgroups of m 3 ¯ m with approximately Ni61.5Ti31Hf7.5 composition .

The deformation mechanisms that dictate the tribological performances of heat treated Ni55Ti45, Ni54Ti45Hf1 and Ni56Ti36Hf8 alloys are revealed through rolling contact fatigue (RCF) testing and transmission electron microscopy (TEM) analyses. Analysis of worn samples that passed a 5×108 cycle RCF runout condition shows that damage is primarily confined to deformation bands that propagate several hundred nanometers – to – several microns beneath the surface. These bands nucleate via localization of dislocation slip within the B2 austenite phase of the alloys. For the Ni55Ti45 and Ni54Ti45Hf1 samples, further damage and eventual spall failures occur by shearing and dissolution of the strengthening Ni4Ti3 nanoprecipitates within the deformation bands, followed by nanocrystallization that sometimes includes stress-induced nucleation of B19′ nanocrystals. Eventually, complete amorphization occurs prior to fracture. The relative 15 – 25% increase in RCF contact stress performance of the Ni56Ti36Hf8 alloy correlates with a more limited depth of damaged material beneath the wear surface; heavily damaged material beneath spall failure sites only extends 1.5 µm into the sample, compared to > 6 µm for Ni55Ti45 and Ni54Ti45Hf1 alloys. This superior RCF damage resistance of the Ni56Ti36Hf8 alloy results from a lower fraction of B2 matrix phase (≤ 13 %) that is highly confined by both cubic Ni-rich NiTiHf and H-phase nanoprecipitates. Specifically, this microstructure limits the widths of deformation bands within the B2 austenite phase to less than the size of the strengthening nanoprecipitates, which in turn inhibits precipitate shearing and dissolution processes that precede nanocrystallization and amorphization.

The effects of refractory ( R ) elements ( R = Re, Ru, W, or Ta) on a base Ni-Al-Cr alloy are studied, for an aging temperature of 1073 K (800 °C) and an aging time of 256 h, employing atom-probe tomography (APT) and first-principles calculations. We find that there are strong attractive chemical binding energies between R -elements and solute ( S ) atoms ( S = Al, Cr) in Ni-Al-Cr based alloys utilizing experimental partial radial distribution function (RDF) results, and first-principles calculations performed at 0 K. We demonstrate that correlated R - S binding energies play a key role in the observed Ni retention-excesses at γ(f.c.c.)/γ′(L1 2 -structure) interfaces at aging times as long as 256 h. The total reduction of the γ(f.c.c.)/γ′(L1 2 ) interfacial energy, as a result of Ni interfacial-excesses in both γ(f.c.c.)-matrix and γ′(L1 2 )-precipitates, lies between −0.16 ± 0.06 mJ m −2 and −0.05 ± 0.02 mJ m −2 . The R - S binding energies cause changes in the compositional diffusion flux-vectors in and out of γ′(L1 2 )-precipitates, which result in larger solvent Ni retention-excesses and wider interfacial compositional widths at 256 h, when compared with the base Ni-Al-Cr alloy. Refractory elements are slow diffusers in nickel and the attractive R -Cr binding energies decelerate the solute diffusional fluxes, which results in a decrease of the Ni diffusivity, which in turn hinders the flux of Ni atoms away from the γ(f.c.c.)/γ′(L1 2 ) interfaces.

The effects of heat treatment on the shape memory characteristics of a polycrystalline Ni50.3Ti29.7Hf20 alloy were studied via thermal cycling under stress and isothermal stress cycling experiments in tension. It was revealed that transformation temperatures could be increased above 100 °C with aging at temperature above 500 °C and in particular were stabilized against stress-free thermal cycling after aging at 500 °C. Recoverable strain of ~ 5% was observed for the as-extruded samples and decreased to ~ 4% after aging due to the formation of non-transformable precipitates. The aged alloys demonstrated near perfect shape memory effect under tensile stresses as high as 700 MPa and perfect superelasticity at temperatures up to 230 °C. Finally, the tension-compression asymmetry observed in NiTiHf alloys was discussed.

A general procedure to optimize shape memory alloys (SMAs) for specific engineering performance metrics is outlined and demonstrated through a study of ternary, NiTiX high-temperature SMAs, where X = Pd, Hf, Zr. Transformation strains are calculated using the crystallographic theory of martensite and compared to the cofactor conditions, both requiring only lattice parameters as inputs. Measurements of transformation temperatures and hysteresis provide additional comparisons between microstructural-based and transformation properties. The relationships between microstructural-based properties and engineering performance metrics are then thoroughly explored. Use of this procedure demonstrates that SMAs can be tuned for specific applications using relatively simple, fast, and inexpensive measurements and theoretical calculations. The results also indicate an overall trade-off between compatibility and strains, suggesting that alloys may be optimized for either minimal hysteresis or large transformation strains and work output. However, further analysis of the effects of aging shows that better combinations of uncompromised properties are possible through solid solution strengthening.

The relationship between precipitate evolution, martensitic transformation temperatures, hardness, and functional load-bias behavior has been analyzed for a Ni50.8Ti34.2Zr15 (at.%) alloy. In the solutionized condition, the alloy was fully austenitic and no transformation (at least to −90 °C) was observed. Upon aging at 550 °C, the onset of a martensitic transformation (Ms), as determined by differential scanning calorimetry, was observed at approximately −10 °C and 75 °C after 24 and 300 h, respectively. Electron diffraction identified the precipitation of the orthorhombic H-phase within the B2 matrix. When the inter-precipitate spacing was ~12 nm, a greater undercooling was necessary to initiate the martensitic transformation due to overlapping strain fields of the precipitates. As the precipitates coarsened with aging time, a corresponding increase in the inter-precipitate spacing occurred and the chemical partitioning effects between the matrix and precipitate, as determined by atom probe tomography, began to dominate the transformation behavior resulting in an increase in transformation temperatures. For selected aging conditions, the load-biased shape memory behavior was determined under compressive and tensile loading using uniaxial constant-force thermal cycling experiments. A tension-compression asymmetry was noted with larger transformation strains in tension than compression at constant stresses up to 400 MPa. A recoverable transformation strain of 3% was observed in the sample aged for 4 h at 550 °C under a tensile stress of 400 MPa, which is the largest recoverable strain currently reported for a precipitation-strengthened NiTiZr alloy.

A "cubic Ni3Ti2" precipitate phase recently reported to exist within NiTi and NiTiNb alloys is documented to also form within a Ni56Ti36Hf8 alloy upon aging. Using transmission electron microscopy and ab intio density functional theory techniques, the phase is more precisely identified to be Ni16Ti11 with symmetry of the pm3m space group and a lattice parameter a = 8.816 A. In this structure, nickel atoms preferentially segregate to the perimeter lattice sites of the 54-atom unit cell.

A series of Ti-rich Ni-Ti-Pt ternary alloys with 13 to 18 at. pct Pt were processed by vacuum arc melting and characterized for their transformation behavior to identify shape memory alloys (SMA) that undergo transformation between 448 K and 498 K (175 °C and 225 °C) and achieve recoverable strain exceeding 2 pct. From this broader set of compositions, three alloys containing 15.5 to 16.5 at. pct Pt exhibited transformation temperatures in the vicinity of 473 K (200 °C), thus were targeted for more detailed characterization. Preliminary microstructural evaluation of these three compositions revealed a martensitic microstructure with small amounts of Ti2(Ni,Pt) particles. Room temperature mechanical testing gave a response characteristic of martensitic de-twinning followed by a typical work-hardening behavior to failure. Elevated mechanical testing, performed while the materials were in the austenitic state, revealed yield stresses of approximately 500 MPa and 3.5 pct elongation to failure. Thermal strain recovery characteristics were more carefully investigated with unbiased incremental strain-temperature tests across the 1 to 5 pct strain range, as well as cyclic strain-temperature tests at 3 pct strain. The unbiased shape recovery results indicated a complicated strain recovery path, dependent on prestrain level, but overall acceptable SMA behavior within the targeted temperature and recoverable strain range.

A static rock splitter device based on high-force, high-temperature shape memory alloys (HTSMAs) was developed for space related applications requiring controlled geologic excavation in planetary bodies such as the moon, Mars, and near-Earth asteroids. The device, hereafter referred to as the shape memory alloy rock splitter (SMARS), consisted of active (expanding) elements made of Ni50.3Ti29.7Hf20 (at%) that generate extremely large forces in response to thermal input. The pre-shaping (training) of these elements was accomplished using isothermal, isobaric and cyclic training methods, which resulted in active components capable of generating stresses in excess of 1.5 GPa. The corresponding strains (or displacements) were also evaluated and were found to be 2–3%, essential to rock fracturing and/or splitting when placed in a borehole. SMARS performance was evaluated using a testbed consisting of a temperature controller, custom heaters and heater holders, and an enclosure for rock placement and breakage. The SMARS system was evaluated using various rock types including igneous rocks (e.g., basalt, quartz, granite) and sedimentary rocks (e.g., sandstone, limestone).

A series of Ni-rich Nitinol compositions spanning from 53NiTi to 58NiTi (at%) have been solutionized at 1050 °C and aged at 400 °C, 625 °C, and 750 °C for varying times to determine the correlation between microstructure and hardenability. Compositions of 55NiT, 56NiTi, and 57NiTi displayed peak hardness values near 650 VHN upon quenching, which are on par with tool steels. Upon aging at 400 °C, all but the 55NiTi and 56NiTi compositions exhibited a decrease in hardness initiating, between 1 and 10 h for the lower Ni alloys and after 100 h for the highest Ni containing alloys. The high hardness, including the solution treated condition, was attributed to the precipitation of a large volume fraction of nanoscale Ni 4 Ti 3 platelets that resulted in narrow B2 NiTi matrix channels. These channels provided a microstructure-driven strengthening morphology. Upon increasing Ni content to greater than 56NiTi and increasing the aging time and temperature, the Ni 4 Ti 3 phase decomposed to either Ni 3 Ti 2 and/or Ni 3 Ti with a subsequent loss in hardness. The decomposition morphology between the precipitates was characterized by serial sectioning showing that Ni 4 Ti 3 platelets acted as a heterogeneous nucleation site and subsequent Ni-reservoir during the growth of globular Ni 3 Ti precipitates.

Poor machinability with conventional machining processes is a major shortcoming that limits the manufacture of NiTi components. To better understand the effects of phase state on the machining performance of NiTi alloys, cutting temperature, tool-wear behavior, cutting force components, tool-chip contact length, chip thickness, and machined surface quality data were generated from a NiTi alloy using precooled cryogenic, dry, minimum quantity lubrication (MQL), and preheated machining conditions. Findings reveal that machining NiTi in the martensite phase, which was achieved through precooled cryogenic machining, profoundly improved the machining performance by reducing cutting force components, notch wear, and surface roughness. Machining in the austenite state, achieved through preheating, did not provide any benefit over dry and MQL machining, and these processes were, in general, inferior to cryogenic machining in terms of machining performance, particularly at higher cutting speeds.

The temporal evolution of γ′(L12 structure) precipitates is studied in Ni–12.5 at.% Al and Ni–13.4 at.% Al alloys, aged at 823 and 873 K, utilizing three-dimensional atom-probe tomography. The values of the interfacial widths, δ(t)s, between the γ(face-centered cubic) and γ′ phases are calculated utilizing proximity histograms. It is demonstrated that δ(t) decreases continuously with increasing aging time for both Ni–Al alloys: that is, the δ(t)s decrease with increasing mean precipitate radius, 〈 R ( t ) 〉 . The ratio δ ( t ) 〈 R ( t ) 〉 decreases, to first order, as 〈 R ( t ) 〉 - 1 .

Extremely high tool-wear rate in machining of NiTi shape memory alloys (SMAs) is one of the major reasons for limiting the use of conventional machining processes on NiTi. The present study begins to address this issue by examining the effects of cryogenic cooling on tool-wear rate and progressive tool-wear by comparing the new findings from cryogenic machining with results obtained from minimum quantity lubrication (MQL) and dry machining conditions. Flank wear at the nose region, notch wear at the depth of cut boundary, and resulting machining performance criteria such as force components and surface quality of machined samples were studied. The findings from this research demonstrate that cryogenic cooling has a profound effect on controlling tool-wear rate and that the progressive tool-wear in machining of NiTi shape memory alloys can be significantly reduced by cryogenic machining.

Thermal aging of the high-temperature shape memory alloy 50.3Ni–29.7Ti–20Hf (at.%) introduces a novel precipitate phase that plays an important role in improving shape memory properties. The precipitate phase was investigated by conventional electron diffraction, high-resolution scanning transmission electron microscopy (STEM) and three-dimensional atom probe tomography. An unrelaxed orthorhombic atomic structural model is proposed based on these observations. This model was subsequently relaxed by ab initio calculations. As a result of the relaxation, atom shuffle displacements occur, which in turn yields improved agreement with the STEM images. The relaxed structure, which is termed the “H phase”, has also been verified to be thermodynamically stable at 0 K.

The temporal evolution of a Ni–10.0Al–8.5Cr–2.0Ru (at.%) alloy aged at 1073 K was investigated using transmission electron microscopy (TEM) and atom-probe tomography. The γ′(L12)-precipitate morphology is spheroidal through 256 h of ageing as a result of adding Ru, which decreases the lattice parameter misfit between the γ′(L12)- and γ(f.c.c.)-phases. The addition of Ru accelerates the compositional evolution of the γ′(L12)- and γ(f.c.c.)-phases, which achieve their equilibrium compositions after 0.25 h. Initially, Ru accelerates the partitioning of Ni and Cr to the γ(f.c.c.)-phase, and the partitioning of Al to the γ′(L12)-phase, but after 0.25 h, Ru, which partitions to the γ(f.c.c.)-phase, decreases the partitioning of Ni and increases the partitioning of Al and Cr. The temporal evolution of the average radius, ⟨R(t)⟩, number density, volume fraction of the γ′(L12)-precipitates, and the supersaturations of Ni, Al, Cr, and Ru in the γ(f.c.c.)- and γ′(L12)-phases are compared in detail with predictions o...

The present study focuses on tool-wear behaviour and cutting forces in machining of NiTi shape memory alloys (SMAs) under various machining conditions, namely dry, preheated, and cryogenic cooling at three different cutting speeds. Obtained results show that cryogenic cooling plays a significant role on reducing notch wear at higher cutting speeds in comparison with machining under dry and preheated conditions. It is also found that cryogenic cooling substantially decreases the cutting force requirement compared with machining under dry and preheated conditions. Chip thickness is not significantly affected by machining conditions. Based on these experimental findings, cryogenic machining is considered a promising approach for improving machining performance of NiTi shape memory alloys.

The microstructure and properties of a precipitation-hardenable Ni-48Ti-25Pd (at. pct) shape memory alloy have been investigated as a function of various aging conditions. Both the hardness and martensitic transformation temperatures increased with increasing aging time up to 100 hours at 673 K (400 °C), while no discernable differences were observed after heat treatment at 823 K (550 °C), except for a slight decrease in hardness. For aging at 673 K (400 °C), these effects were attributed to the formation of nano-scale precipitates, while precipitation was absent in the 823 K (550 °C) heat-treated specimens. The precipitation-strengthened alloy exhibited stable pseudoelastic behavior and load-biased-shape memory response with little or no residual strains. The precipitates had a monoclinic base-centered structure, which is the same structure as the P-phase recently reported in Ni(Pt)-rich NiTiPt alloys. 3D atom probe analysis revealed that the precipitates were slightly enriched in Ni and deficient in Pd and Ti as compared with the bulk alloy. The increase in martensitic transformation temperatures and the superior dimensional stability during shape memory and pseudoelastic testing are attributed to the fine precipitate phase and its effect on matrix chemistry, local stress state because of the coherent interface, and the ability to effectively strengthen the alloy against slip.

A stable Ni-rich Ni-29.7Ti-20Hf (at. pct) shape memory alloy, with relatively high transformation temperatures, was shown to exhibit promising properties at lower raw material cost when compared to typical NiTi-X (X = Pt, Pd, Au) high-temperature shape memory alloys (HTSMAs). The excellent dimensional stability and high work output for this alloy were attributed to a coherent, nanometer size precipitate phase observed using transmission electron microscopy. To establish an understanding of the role of these precipitates on the microstructure and ensuing stability of the NiTiHf alloy, a detailed study of the micromechanical and microstructural behaviors was performed. In-situ neutron diffraction at stress and temperature was used to obtain quantitative information on phase-specific internal strain, texture, and phase volume fractions during both isothermal and isobaric testing of the alloy. During isothermal testing, the alloy exhibited low isothermal strains due to limited detwinning, consistent with direct measurements of the bulk texture through neutron diffraction. This limited detwinning was attributed to the pinning of twin and variant boundaries by the dispersion of fine precipitates. During isobaric thermal cycling at 400 MPa, the high work output and near-perfect dimensional stability was attributed to the presence of the precipitates that act as homogeneous sources for the nucleation of martensite throughout the material, while providing resistance to irrecoverable processes such as plastic deformation.

The microstructure of 46Ti–37.5Ni–16.5Pd (at.%) alloy was investigated by electron diffraction and high-resolution scanning transmission electron microscopy. The phase content and stability were determined at several different temperatures and times. Aging at 400 °C for 1 h results in a new phase (P1-phase), which is consumed by P-phase at longer aging times. At 450 °C, the P1-phase appears first, and then coexists with P-phase. At 500 °C, the entire alloy transforms into the P1-phase. At 550 °C, Ti3(Ni,Pd)4 phase begins to form.

Over the past decade, interest in shape memory alloy based actuators has increased as the primary benefits of these solid-state devices have become more apparent. However, much is still unknown about the characteristic behavior of these materials when used in actuator applications. Recently we have shown that the maximum temperature reached during thermal cycling under isobaric conditions could significantly affect the observed mechanical response of NiTi (55 wt% Ni), especially the amount of transformation strain available for actuation and thus work output. The investigation we report here extends that original work to ascertain whether further increases in the upper-cycle temperature would produce additional changes in the work output of the material, which has a stress-free austenite finish temperature of 113 C, and to determine the optimum cyclic conditions. Thus, isobaric, thermal-cycle experiments were conducted on the aforementioned alloy at various stresses from 50-300 MPa using upper-cycle temperatures of 165, 200, 230, 260, 290, 320 and 350 C. The data indicated that the amount of applied stress influenced the transformation strain, as would be expected. However, the maximum temperature reached during the thermal excursion also plays an equally significant role in determining the transformation strain, with the maximum transformation strain observed during thermal cycling to 290 C. In situ neutron diffraction at stress and temperature showed that the differences in transformation strain were mostly related to changes in martensite texture when cycling to different upper-cycle temperatures. Hence, understanding this effect is important to optimizing the operation of SMA-based actuators and could lead to new methods for processing and training shape memory alloys for optimal performance.

The influence of inelastic phenomena (i.e. plasticity and viscoplasticity) on the phase transformation and the cyclic actuation behavior of a Ti50.5Pd30Ni19.5 high temperature shape memory alloy (HTSMA) was investigated by thermomechanical testing. Standard creep and constant stress thermal cycling experiments were conducted to study the rate-independent and rate-dependent irrecoverable strain generation both individually and simultaneously with the phase transformation. Based on a preliminary power-law fit of the creep data from the creep tests, the varying creep rates and stress exponents suggest that the mechanism for creep deformation changes with both stress level and temperature within the likely operating range for the alloy. The load-biased thermal cycling tests show that the material performance can be significantly affected by rate independent plasticity strains generated during transformation, rate dependent viscoplastic strains as well as factors such as retained martensite accumulation. To consolidate these inelastic mechanisms, a combined phase transformation–deformation diagram was constructed to show the phase transformation along with the plastic and viscoplastic regions within the operational range of the HTSMA.

A recent microstructure-based FEM model that couples crystal-based plasticity, the B2 MB190 phase transformation and anisotropic elasticity at the grain scale is calibrated to recent data for polycrystalline NiTi (49.9 at.% Ni). Inputs include anisotropic elastic properties, texture and differential scanning calorimetry data, as well as a subset of recent isothermal deformation and load-biased thermal cycling data. The model is assessed against additional experimental data. Several experimental trends are captured - in particular, the transformation strain during thermal cycling monotonically increases and reaches a peak with increasing bias stress. This is achieved, in part, by modifying the martensite hardening matrix proposed by Patoor et al. [Patoor E, Eberhardt A, Berveiller M. J Phys IV 1996;6:277]. Some experimental trends are underestimated - in particular, the ratcheting of macrostrain during thermal cycling. This may reflect a model limitation that transformation-plasticity coupling is captured on a coarse (grain) scale but not on a fine (martensitic plate) scale.