Ni Ti Hf Research Articles

Microstructure and Thermoelastic Martensitic Transformation in Ni-Low and -Rich Ni–Ti–Hf–Nb Hightemperature Shape Memory Alloys

Microstructure and Thermoelastic Martensitic Transformation in Ni-Low and -Rich Ni–Ti–Hf–Nb Hightemperature Shape Memory Alloys

Functional Properties of a Ni-rich Ni–Ti–Hf Shape Memory Alloy Fabricated via Laser Beam Powder Bed Fusion—Impact of Porosity and Precipitation Characteristics on the Thermal Hysteresis

Additive manufacturing (AM) is very promising for the fabrication of complex parts made from shape memory alloys (SMAs). In the present study, a Ni–Ti–Hf shape memory alloy has been processed by laser beam powder bed fusion of metals (PBF-LB/M). Employing different sets of processing parameters, i.e., a variation of scanning speed, specimens characterized by various microstructures and porosities were obtained. Microstructural analysis revealed that processing of Ni–Ti–Hf SMAs at a low energy level promotes the formation of a fine-grained microstructure with numerous lack of fusion defects. Transmission electron microscopy (TEM) studies revealed that H-phase precipitates are present in any case, leading to an increase in the Ms-temperature and, thus, a phase transformation at room temperature. The thermal stability of the phase transformation behavior in different Ni–Ti–Hf as-built conditions was studied using differential scanning calorimetry (DSC). DSC analysis showed that specimens with a higher defect density are characterized by smaller thermal hysteresis.

Application of CALPHAD Method for Predicting of Concentration Range of Amorphization of Transition Metals Melts

Early, the efficiency of the CALPHAD (Calculation of Phase Diagrams) method to a targeted search for compositions of amorphous alloys has been shown. The method for predicting the ranges of amorphization is based on the calculation of diagrams of metastable phase transformations between supercooled melts and boundary solid solutions on the base of pure elements. In this work, the model parameters for thermodynamic properties of liquid alloys and boundary solid solutions were summarized in a self-consistent database for the multicomponent Cu–Fe–Ni–Ti–Zr–Hf system. Such database for the multicomponent system is based on a common set of model parameters for boundary binary and ternary systems. This database was used to predict the concentration ranges of amorphization for the quinary Cu–Fe–Ni–Ti–Zr, Cu–Fe–Ni–Ti–Hf and boundary ternary and quaternary systems. The results of calculations are presented along sections in quaternary and quinary systems. The ternary and quaternary equiatomic alloys along with high entropy CuFeNiTiZr and CuFeNiTiHf alloys are trapped into prognosed composition ranges of amorphization. Predicted composition space of amorphization for melts of the Fe–Ni–Ti–Zr system is shown on the concentration tetrahedron. Based on the obtained results, a new criterion for predicting the concentration regions of amorphization of multicomponent melts is proposed, according to which the presence of a sufficient content of metals that are electron acceptors and donors is a chemical factor that affects the thermodynamic stability of melts and determines their glass-forming ability. For multicomponent melts of the Cu–Fe–Ni–Ti–Zr–Hf system the concentration ranges of amorphization correspond to the simultaneous fulfillment of the conditions xFe + xNi + xCu > 0.25 and xTi + xZr + xHf > 0.15, where Fe, Ni, and Cu are electron acceptors and Ti, Zr, and Hf are electron donors.

Thermodynamic modeling of the Ni–Ti–Hf system

Ni–Ti–Hf alloys have received extensive attention owing to their excellent shape-memory behavior. In the present work, the thermodynamic assessment of the Ni–Ti–Hf system was performed using the CALPHAD method after a critical review of the thermodynamic descriptions of boundary binaries and available experimental data in the ternary system. The solubility ranges of the third elements in binary intermetallic compounds are well described. Moreover, the wide homogeneity ranges of the B2 and NiTi2 phases are satisfactorily reproduced. The ternary τ phase was reasonably described using a two-sublattice model (Ni)0.44(Hf,Ti)0.56. Both the thermochemical properties and phase diagrams were well described using the present model parameters.

Optimization of wire-EDM process parameters for Ni–Ti-Hf shape memory alloy through particle swarm optimization and CNN-based SEM-image classification

Shape memory alloys (SMAs) have the unique ability to regain their shape under specified conditions, making them extremely useful for a wide range of applications. However, non-traditional machining techniques could be more effective for high-temperature SMAs as they provide better shape recovery properties than conventional methods, necessitating this study's unconventional wire electric discharge machining procedure. The surface morphology of Ni–Ti-Hf-based alloys was examined using scanning electron microscopy. A convolutional neural network model was used to categorize SEM images based on the material removal rate, utilizing the pixel intensity histogram of the processed images. The study discovered that the material remelted as the discharge energy increased, leaving lumps and globules on the surface. The size of debris lumps, pores, and globules increased with increasing Ra values. Moreover, widening the inter-electrode gap by expanding the servo-voltage facilitated efficiently removing debris from the machined site. The TOPSIS method for particle swarm optimization was employed to find the optimal solutions, yielding TON = (124.239, 116.228), TOFF = (54.532, 40.781), Servo voltage = (36.216, 43.766), and Wire-Feed = (2.157, 8). These results were validated through experimentation, with minimal error percentages of 2.01%, 2.046% (MRR), and 3.86%, 1.611% (Ra) for both sets of input parameters, respectively.

Thermodynamic assessment of the ternary Ni–Ti-Hf system

The Ni–Ti-Hf ternary system has been assessed by CALPHAD method combined with first-principles calculations. Based on experimental results in the literature, the whole system is evaluated completely. The liquid, γ-Ni, β-(Hf, Ti), α-(Hf, Ti) are modeled using the substitution solution model. Ordered and disordered bcc phases use single Gibbs energy description, while the other intermetallic compounds use corresponding sublattice model to describe. The formation enthalpies of the hypothetical end members of each phase in Ni–Ti-Hf ternary system have been calculated using first principles and incorporated into the modeling. According to the experimental results, the sublattice model of the newly discovered ternary phase τ is determined as (Ni)11(Hf, Ti)14 and the phase is added to the thermodynamic optimization. By comparing the experimental data with the calculated results, the thermodynamic description of this work is in good agreement with the reasonable experimental results. The calculated Ni–Ti-Hf ternary system is summarized by means of isothermal sections, vertical sections, liquidus projection and reaction scheme.

Crystal-plasticity modeling of phase transformation–viscoplasticity coupling in high-temperature shape memory alloys

A coupling between phase transformation and viscoplasticity is observed in HTSMAs during actuation. The dislocations generated and retained phases accumulated are responsible for the coupling. It results in functional fatigue, which is reflected as an alteration in the functional properties of the alloy, and an increase in the irrecoverable deformations. The objective of the present study was to develop a theoretical framework to account for the interactions between viscoplasticity and phase transformation to simulate the alteration in functional properties and generation of irrecoverable deformations. A crystal-plasticity based multi-scale approach was followed to develop the framework. This approach accounts for the mechanisms of: phase transformation, transformation induced plasticity, accumulation of retained martensite, plasticity (in a rate-independent manner), and viscoplasticity (in a rate-dependent manner). The coupling was accounted by a direct effect of the dislocation densities produced by the irrecoverable mechanisms onto the transformation resistance and retained martensite. This resulted in an indirect effect on the functional properties of phase transformation. On simulating the response of single crystals and polycrystals, anisotropic responses are captured at the grain scale (from single crystals), and a nearly isotropic response is captured at the macro scale (from polycrystals). The results show consistency between the functional property trends (such as TT and hysteresis) and those observed experimentally at the macroscale. The contributions of this study are presenting an effect of: (i) texture, (ii) thermal cycling rate and (iii) functional fatigue, through the response of several randomly oriented single crystals and a polycrystal of Ni–Ti–Hf HTSMA.

Ni–Ti-Hf high-temperature shape memory alloy: Measure of the Clausius-Clapeyron coefficient through mechanical spectroscopy

The martensitic transformation of Ni49.5Ti35.5Hf15 high temperature shape memory alloy is characterized by internal friction measurements. The temperatures for the reversible B2 ↔ B19’ transformation appear in the range 410–479 K on cooling and 447–526 K on heating. In addition, a strong anomalous pre-martensitic softening of the dynamic modulus is reported in the high-temperature phase, between 850 K and 550 K, evidencing the thermoelastic character of this family of alloys. Based on the analysis of the internal friction spectra, a theoretical and experimental methodology is proposed to measure the Clausius-Clapeyron coefficient through mechanical spectroscopy. This new non-destructive method could be extremely useful for the development of advanced prototypes of shape memory alloys.

Study of the Structure and Properties of High-Temperature Shape-Memory Alloys of the Ti–Pd–Ni and Ni–Ti–Hf Systems

Abstract—Comprehensive studies on retrieving information about the elemental and local phase composition, phase transition temperatures, and mechanical and thermomechanical characteristics of high-temperature shape-memory alloys of the Ti–Pd–Ni and Ni–Ti–Hf systems in the as-received condition and after thermal treatment have been carried out. The results of this study are necessary for the development of various safety devices used in nuclear power facilities.

H-Phase Precipitation and Martensitic Transformation in Ni-rich Ni–Ti–Hf and Ni–Ti-Zr High-Temperature Shape Memory Alloys

The distributions of H-phase precipitates in Ni50.3Ti29.7Hf20 and Ni50.3Ti29.7Zr20 alloys formed by aging treatments at 500 and 550 °C or slow furnace cooling and their effects on the thermal martensitic transformation have been investigated by TEM and calorimetry. The comparative study clearly reveals faster precipitate-coarsening kinetics in the NiTiZr alloy than in NiTiHf. For precipitates of a similar size of 10–20 nm in both alloys, the martensite plates in Ni50.3Ti29.7Zr20 have larger widths and span a higher number of precipitates compared with the Ni50.3Ti29.7Hf20 alloy. However, for large H-phase particles with hundreds of nm in length, no significant differences in the martensitic microstructures of both alloy systems have been observed. The martensitic transformation temperatures of Ni50.3Ti29.7Hf20 are ~ 80–90 °C higher than those of Ni50.3Ti29.7Zr20 in the precipitate-free state and in the presence of large particles of hundreds on nm in length, but this difference is reduced to only 10–20 °C in samples with small H-phase precipitates. The changes in the transformation temperatures are consistent with the differences in the precipitate distributions between the two alloy systems observed by TEM.

Crystallization and microstructural evolution of an amorphous Ni–Ti–Hf film

An amorphous Ni–Ti–Hf film was fabricated through DC magnetron sputtering deposition. The crystallization and microstructural evolution of the amorphous Ni–Ti–Hf film was observed via in situ transmission electron microscopy. Composition segregation occurred after crystallization for different grains. The grains showed two phases, namely, B19′ martensite for Ni49.78Ti35.13Hf15.09 and B2 austensite for Ni55.36Ti31.08Hf13.56 at room temperature.

Microstructure evolution and phase transformation in thermally cycled Ni–Ti–Hf film

A Ni[Formula: see text]Ti[Formula: see text]Hf[Formula: see text] film was synthesized through magnetron sputtering followed by crystallization and thermal cycling. Microstructure evolution and phase transformation were investigated through transmission electron microscopy and differential scanning calorimetry. Crystallization can be partially completed when heating temperature was increased to 540[Formula: see text]C, which is higher than the usually thought crystallization temperature of 503.6[Formula: see text]C. After crystallization occurs, the film consists of large Ni–Ti–Hf grains and small granular particles of (Ti,[Formula: see text]Hf)2Ni precipitates dispersed in an amorphous pattern. As the number of thermal cycles increases, crystallization is completed gradually and martensite transformation temperature decreases gradually.

Structure and thermoelastic martensitic transformations in ternary Ni–Ti–Hf alloys with a high-temperature shape memory effect

The effect of alloying by 12–20 at % Hf on the structure, the phase composition, and the thermoelastic martensitic transformations in ternary alloys of the quasi-binary NiTi–NiHf section is studied by transmission electron microscopy, scanning electron microscopy, electron diffraction, and X-ray diffraction. The electrical resistivity is measured at various temperatures to determine the critical transformation temperatures. The data on phase composition are used to plot a full diagram for the high-temperature thermoelastic B2 ↔ B19’ martensitic transformations, which occur in the temperature range 320–600 K when the hafnium content increases from 12 to 20 at %. The lattice parameters of the B2 and B19’ phases are measured, and the microstructure of the B19’ martensite is analyzed.

A procedure to create isoconcentration surfaces in low-chemical-partitioning, high-solute alloys

A proximity histogram or proxigram is the prevailing technique of calculating 3D composition profiles of a second phase in atom probe tomography. The second phase in the reconstruction is delineated by creating an isoconcentration surface, i.e. the precipitate–matrix interface. The 3D composition profile is then calculated with respect to this user-defined isoconcentration surface. Hence, the selection of the correct isoconcentration surface is critical. In general, the preliminary selection of an isoconcentration value is guided by the visual observation of a chemically partitioned second phase. However, in low-chemical -partitioning systems, such a visual guide is absent. The lack of a priori composition information of the precipitate phase may further confound the issue. This paper presents a methodology of selecting an appropriate elemental species and subsequently obtaining an isoconcentration value to create an accurate isoconcentration surface that will act as the precipitate–matrix interface. We use the H-phase precipitate in the Ni–Ti–Hf shape memory alloy as our case study to illustrate the procedure.

Application of in-situ nano-scanning calorimetry and X-ray diffraction to characterize Ni–Ti–Hf high-temperature shape memory alloys

Combinatorial nanocalorimetry and synchrotron X-ray diffraction were combined to study the martensite–austenite (M–A) phase transformation behavior of Ni–Ti–Hf shape memory alloys. A thin-film library of Ni–Ti–Hf samples with a range of compositions was deposited on a parallel nano-scanning calorimeter device using sputter deposition. Crystallization of each amorphous as-deposited sample by local heating at approximately 104K/s produced a nanoscale grain structure of austenite and martensite. Individual samples were then cycled through the M–A transformation, while the transformation enthalpy was measured by nanocalorimetry and the low- and high-temperature phase compositions were determined by X-ray diffraction. The techniques enable correlation of the observed behavior during thermal cycling with the thermodynamic and structural properties of the samples.

TEM study of structural and microstructural characteristics of a precipitate phase in Ni-rich Ni–Ti–Hf and Ni–Ti–Zr shape memory alloys

The precipitates formed after suitable thermal treatments in seven Ni-rich Ni–Ti–Hf and Ni–Ti–Zr high-temperature shape memory alloys have been investigated by conventional and high-resolution transmission electron microscopy. In both ternary systems, the precipitate coarsening kinetics become faster as the Ni and ternary element contents (Hf or Zr) of the bulk alloy are increased, in agreement with the precipitate composition measured by energy-dispersive X-ray microanalysis. The precipitate structure has been found to be the same in both Hf- and Zr-containing ternary alloys, and determined to be a superstructure of the B2 austenite phase, which arises from a recombination of the Hf/Zr and Ti atoms in their sublattice. Two different structural models for the precipitate phase were optimized using density functional theory methods. These calculations indicate that the energetics of the structure are not very sensitive to the atomic configuration of the Ti–Hf/Zr planes, thus significant configurational disorder due to entropic effects can be envisaged at high temperatures. The precipitates are fully coherent with the austenite B2 matrix; however, upon martensitic transformation, they lose some coherency with the B19′ matrix as a result of the transformation shear process in the surrounding matrix. The strain accommodation around the particles is much easier in the Ni–Ti–Zr-containing alloys than in the Ni–Ti–Hf system, which correlates well with the lower transformation strain and stiffness predicted for the Ni–Ti–Zr alloys. The B19′ martensite twinning modes observed in the studied Ni-rich ternary alloys are not changed by the new precipitated phase, being equivalent to those previously reported in Ni-poor ternary alloys.

Thermomechanical training and characterization of Ni–Ti–Hf and Ni–Ti–Hf–Cu high temperature shape memory alloys

Nickel–titanium (NiTi) is the most commonly used shape memory alloy (SMA) for actuator applications, though its usefulness is limited to temperature ranges below 100 °C. High temperature SMAs are formed by adding ternary elements to NiTi, but their usefulness as actuators is still in question. The purpose of this research was to characterize and train two high temperature SMAs, NiTi29.7Hf20 and NiCu5Ti29.7Hf20, to determine their effectiveness as linear actuators. Low temperature martensitic phase and high temperature austenitic phase stress–strain tests were performed to characterize the materials’ behavior followed by temperature cycling under constant stress. Temperature cycling under constant stress is known as thermomechanical training and resulted in small amounts of plastic strain growth and the development of two-way shape memory (TWSM). The results from these tests support the conclusion that hafnium distorts slip planes within the martensitic material phase, and that (Ti,Hf)2Ni and (Ti,Hf)3Ni4 particulates form during aging and annealing. The distorted slip planes cause slip and martensite reorientation to occur simultaneously, which develops a strong internal stress field during training within the first few cycles. The internal stress field develops TWSM, but limits further plastic growth. The particulate formation also embrittles the material. The transformation temperatures of both alloys were below creep and annealing temperatures making them ideally suited for high temperature actuators.

Atomistic modeling of ternary additions to NiTi and quaternary additions to Ni–Ti–Pd, Ni–Ti–Pt and Ni–Ti–Hf shape memory alloys

The behavior of ternary and quaternary additions to NiTi shape memory alloys is investigated using a quantum approximate method for the energetics. Ternary additions X to NiTi and quaternary additions to Ni–Ti–Pd, Ni–Ti–Pt, and Ni–Ti–Hf alloys, for X=Au, Pt, Ir, Os, Re, W, Ta,Ag, Pd, Rh, Ru, Tc, Mo, Nb, Zr, Zn, Cu, Co, Fe, Mn, V, Sc, Si, Al and Mg are considered. Bulk properties such as lattice parameter, energy of formation, and bulk modulus of the B2 alloys are studied for variations due to the presence of one or two simultaneous additives.

Nanoindentation of binary and ternary Ni–Ti-based shape memory alloy thin films

Thin sputtered films of binary (Ni–Ti) and ternary (Ni–Ti–Hf and Ni–Ti–Cu) shape memory alloys have been subjected to nanoindentation over a range of temperature (up to 400 °C), using a small diameter spherical indenter. The load-displacement plots obtained during these experiments have been interpreted so as to reveal whether the imposed strain was being at least partly accommodated by the martensitic phase transformation, ie whether superelastic deformation was taking place. This was done by evaluating the remnant indent depth ratio (depth after unloading/depth at peak load), which is expected to have a relatively small value if superelastic deformation and recovery are significant. It is confirmed that this procedure, which has previously been validated for bulk material, can be applied to these thin films (~ 2 µm in thickness). The results indicate that ternary alloys with up to about 20 at.%Hf or 10 at.%Cu can exhibit superelastic behaviour over suitable temperature ranges.

Sputter alloying of Ni, Ti and Hf for fabrication of high temperature shape memory thin films

In the present paper, the fabrication and characterisation of typical high temperature Ni(Ti+Hf) alloyed thin films produced by simultaneous sputter deposition from separate elemental Ni, Ti and Hf targets are presented. Film composition, determined by energy dispersive X-ray spectroscopy, was controlled by adjusting the ratio of powers applied to each target. Films deposited at room temperature had an amorphous structure and subsequent annealing at 550°C was carried out in a high vacuum environment, based on crystallisation temperature evaluation by differential scanning calorimetry (DSC). High temperature martensitic transformation, confirmed by DSC and variable temperature X-ray diffraction (XRD), was achieved by deposition of (Ti+Hf) rich Ni–Ti–Hf films. Any slight change of composition towards Ni rich reduced the transformation temperature. Atomic force microscopy and XRD illustrated that the films had a fine grain structure (∼100 nm). One way shape memory effect was observed at ∼200°C in a film with composition of 15·6 at.-%Hf.