Strain glass in Fe-doped Ti–Ni

We report the existence of strain glass in Ti₅₀Ni_50?xFe_x, beyond a critical Fe doping level x > x_c(5 < x_c < 6). The strain glass state is confirmed by the appearance of a frequency-dependent anomaly in the AC mechanical modulus/loss at a freezing temperature T₀ and by the breaking of ergodicity shown in a zero-field-cooling/field-cooling experiment. Based on the experimental results, a phase diagram is established in which both the normal martensitic transformations (for x < x_c) and the strain glass transition (for x > x_c) are indicated. The new phase diagram allows for explanations of two long-standing puzzles in Ti₅₀Ni_50?xFe_x and Ti–Ni alloys: (i) the origin of nano-domains present prior to the martensitic transformation (for x < x_c) and (ii) the negative temperature dependence of electrical resistivity in abnormal non-transforming compositions (for x > x_c).     

Comparison of high temperature shape memory behaviour for ZrCu-based,Ti–Ni–Zr and Ti–Ni–Hf alloys

New ZrCu-based high temperature shape memory alloys with M_s close to 500 K are under development. The shape memory behaviour of this material is compared to those of Ti–Ni–Zr and Ti–Ni–Hf alloys. The optimal compositions show a shape recovery of not less than 3% at temperatures above 470 K.     

Phase equilibria in Ti–Ni–Pt ternary system

Phase equilibria in Ti–Ni–Pt ternary system have been experimentally determined through diffusion triple technique combined with alloy samples approach. Assisted with electron probe microanalysis (EPMA) and X-ray diffraction (XRD) techniques, isothermal sections at 1073 and 1173 K of this system were constructed and existence of ternary phase Ti₂(Ni,Pt)₃ was confirmed. In addition, binary compounds Ti₃Pt₅ and TiPt_3– were found to be stable at 1073 and 1173 K, and remarkable ternary solubility in some binary compounds was detected, e.g., solubility of Pt in TiNi can be up to about 36% (molar fraction) at 1073 K and 40% (molar fraction) at 1173 K. Furthermore, a ternary invariant transition reaction TiNi₃+Ti₃Pt₅→Ti₂(Ni,Pt)₃+TiPt₃₊ at a temperature between 1073 and 1173 K was deduced.     

Martensite structure in Ti–Ni–Hf–Cu quaternary alloy ribbons containing (Ti,Hf)2Ni precipitates

The martensite structure in a Ti₃₆Ni₄₄Hf₁₅Cu₅ ribbon annealed at different temperatures is investigated. When the annealing temperature is <873 K, spherical (Ti,Hf)₂Ni particles 20–40 nm in diameter precipitate in the grain interior. Transmission electron microscopy analysis shows that (0 0 1) compound twins are dominant in the ribbon containing homogeneously distributed (Ti,Hf)₂Ni precipitates. When the annealing temperature is 773 K, the boundaries between the martensite domains with the (0 0 1) twins are blurry and vague. When the annealing temperature is 873 K, four types of boundaries among the martensite domains are found: {1 1 1}, (0 0 1)//{1 1 1}, {1 1 3} and (1 1 0)//{1 1 3} types. When the annealing temperature is 973 K, the (0 1 1) twins become dominant, and the martensite variants show mainly spear-like and mosaic-like morphologies. However, martensite domains with (0 0 1) twins also exist around the coarse (Ti,Hf)₂Ni precipitates. Fine (Ti,Hf)₂Ni precipitates should be responsible for the improvement in shape memory effect and the superelasticity of Ti–Ni–Hf–Cu ribbons.     

Ti–Cu–Ni shape memory bulk metallic glass composites

New Ti–Cu–Ni shape memory bulk metallic glass composites were obtained by carefully controlling the cooling rate upon quenching. This allows for the formation of a metastable microstructure consisting mainly of ductile, spherical martensitic Ti(Ni,Cu) precipitates embedded in an amorphous matrix also containing a small volume fraction of TiCu and Ti₂Cu precipitates. These composites exhibit large ductility and high strength combined with a strong work-hardening behaviour. A deformation mechanism is proposed with the help of experimental observations and finite-element simulation. The simulation results demonstrate that stress concentrations occur around the precipitates, which promotes a heterogeneous stress distribution and the formation of multiple shear bands. Additionally, different transformation temperatures were observed for martensitic precipitates depending on whether they are completely or partially embedded in the amorphous matrix.     

Machining of a Zr–Ti–Al–Cu–Ni metallic glass

Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ metallic glass machining chips were characterized using SEM, X-ray diffraction and nano-indentation. Above a threshold cutting speed, oxidation of the Zr produces high flash temperatures and causes crystallization. The chip morphology was unique and showed the presence of shear bands, void formation and viscous flow.     

Fatigue behavior of Zr–Ti–Ni–Cu–Be bulk-metallic glasses

The high-cycle fatigue (HCF) behavior of the Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 (in at.%) bulk-metallic glass (BMG) was studied. Two batches of samples that are from different lots (Batches 59 and 94) are employed in present experiments. The HCF experiments were conducted, using an electrohydraulic machine at a frequency of 10 Hz with a R ratio of 0.1 in air at room temperature and under tension-tension loading, where R=σ_min./σ_max.. (σ_min. and σ_max. are the applied minimum and maximum stresses, respectively). A high-speed and high-sensitivity thermographic-infrared (IR) imaging system was employed for the nondestructive evaluation of temperature evolutions during fatigue testing. No distinct sparking phenomenon was observed at the final fracture moment for this alloy. The fatigue lifetime of Batch 59 is longer than that of Batch 94 at high stress levels (maximum stresses >864 MPa). Moreover, the fatigue-endurance limit of Batch 59 (703 MPa) is somewhat greater than that of Batch 94 (615 MPa). The vein pattern and liquid droplets were observed in the apparent-melting region along the edge of the fractured surfaces. The fracture morphology suggests that fatigue cracks initiated from casting defects, such as porosities and inclusions, which have an important effect on the fatigue behavior of BMGs.     

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.     

Development of freeform fabrication method for Ti–Al–Ni intermetallics

A new droplet-based reactive rapid prototyping (RRP) method for making intermetallic parts is demonstrated. This method combines the processes of solid freeform fabrication (SFF) and combustion synthesis (CS). Intermetallic beads are produced by the CS reaction. These synthesized beads are assembled and joined by using the SFF technique with the aid of heat released from exothermic reactions. The intermetallic compound of Ti–Al–Ni is chosen to demonstrate this method. Ni was added to the Ti–Al system to enhance the reaction. Thermodynamics of the Ti–Al–X·NI (X=5, 10, 15 wt.%) system are calculated. The effects of the addition of Ni in powder bed and heating temperature of aluminum droplets on the width and thickness of the reacted area were investigated. As an example, a Ti–Al–Ni intermetallic bar with simple shape was fabricated as a demonstration of RRP.     

Structure of martensite in sputter-deposited (Ni,Cu)-rich Ti–Ni–Cu thin films containing Ti(Ni,Cu)2 precipitates

The martensite structure in sputter-deposited thin films of Ti_48.6Ni_35.9Cu_15.5 was studied. The Ti(Ni,Cu)₂ phase precipitates during the annealing process. Fine Ti(Ni,Cu)₂ precipitates can be deformed by the shear deformation of martensitic transformation, but they obstruct the movement of the twin boundaries to some extent. Coarse Ti(Ni,Cu)₂ precipitates seriously impede the growth of martensite plates and lead to a rectangular-cell-like structure of martensite in the film annealed at 873 K. The resistance of Ti(Ni,Cu)₂ precipitates to the growth of the martensite plates enhances with the coarsening of Ti(Ni,Cu)₂ precipitates, which is one of the reasons for the decrease in the maximum recoverable strain with increasing annealing temperature. B19′ martensite with (0 0 1) compound twinning is frequently observed near coarse Ti(Ni,Cu)₂ precipitates and grain boundaries in films annealed at 873 and 973 K. The local stress concentration should be responsible for the presence of B19′ martensite.     

Transformation-induced plasticity during pseudoelastic deformation in Ni–Ti microcrystals

[1 1 0]-oriented microcrystals of solutionized 50.7 at.% Ni–Ti were prepared by focused ion beam machining and then tested in compression to investigate the stress-induced B2-to-B19′ transformation in the pseudoelastic regime. The compression results indicate a sharp onset of the transformation, consistent with little prior plasticity. Post-mortem scanning transmission electron microscopy reveals no apparent retained martensite but rather a macroscopic band of dislocation activity within which are planar arrays of ～100 nm dislocation loops involving a single a〈0 1 0〉{1 0 1} slip system. Micromechanics analyses show that the angle of the band is consistent with activation of a favored martensite plate. Further, the stress from the individual variants within the plate is shown to favor activation of the observed slip system. The work done by the applied stress during the B2-to-B19′ transformation is estimated to be ～34 MJ m^?3 at ambient temperature.     

Air Oxidation of Ni–Ti Alloys at 650–850°C

The oxidation of pure Ni and three Ni–Ti alloys containing 5, 10, and 15 wt.% Ti over the temperature range 650–850°C in air was studied to examine the effect of titanium on the oxidation resistance of pure nickel. Ni–5Ti is a single-phase solid solution, while the other two alloys consisted of nickel solid solution (-Ni) and TiNi₃. The oxidation of Ni–Ti alloys at 650°C follows an approximately parabolic rate law and produces a decrease in the oxidation rate of pure Ni by forming an almost pure TiO₂ scale. At higher temperatures, Ni–Ti alloys also follow an approximately parabolic oxidation, and their oxidation rates are close to or faster than those of pure Ni. Duplex scales containing NiO, NiTiO₃ and TiO₂ formed. Some internal oxides of titanium formed, especially at 850°C. In addition, the two-phase structure of Ni–10Ti and Ni–15Ti was transformed into a single-phase structure beneath the scales.     

Microstructures of Ti–Ni–Fe wire after severe cold-drawing and annealing

The microstructures and mechanical properties of Ti–47 at%Ni–3 at%Fe shape memory alloy wire under the condition of severe cold-drawing at room temperature and different postdeformation annealing processes were intensively investigated using transmission electron microscope(TEM),X-ray diffraction(XRD),Vickers microhardness tester and electron tensile tester.It is indicated that the structure of the alloy evolves into a predominant amorphous structure with a trace of nanocrystalline B2 phase after the cold-drawing of 76%areal reduction.Postdeformation annealing process exerted significant influence on the microstructure and mechanical properties.Crystallization occurs when the cold-drawn wire was annealed at 300℃ for 30 min.The ultimate tensile strength and ductility as well as the superelasticity of the wire are improved significantly by cold-drawing plus postdeformation annealing.     

Estimation of Transformation Temperatures in Ti–Ni–Pd Shape Memory Alloys

The present study focused on estimating the complex nonlinear relationship between the composition and phase transformation temperatures of Ti–Ni–Pd shape memory alloys by artificial neural networks (ANN). The ANN models were developed by using the experimental data of Ti–Ni–Pd alloys. It was found that the predictions are in good agreement with the trained and unseen test data of existing alloys. The developed model was able to simulate new virtual alloys to quantitatively estimate the effect of Ti, Ni, and Pd on transformation temperatures. The transformation temperature behavior of these virtual alloys is validated by conducting new experiments on the Ti–rich thin film that was deposited using multi target sputtering equipment. The transformation behavior of the film was measured by varying the composition with the help of aging treatment. The predicted trend of transformational temperatures was explained with the help of experimental results.     

In situ formed Ti–Cu–Ni–Sn–Ta nanostructure-dendrite composite with large plasticity

A group of Ti–Cu–Ni–Sn–Ta multicomponent alloys is prepared by copper mold casting and arc melting, respectively, in which nanostructured (or ultrafine-grained) matrix-dendrite composites can be obtained. With increasing Ti and Ta contents, the volume fraction of the dendritic phase increases. The grain size of the matrix phase depends on the preparation method, and is 30–70 nm for as-cast 2–3 mm diameter cylinders and about 100–200 nm for the as-arc melted samples. Compression test results indicate that fully nanostructured samples exhibit very high yield strength of 1800 MPa with a limited plastic strain of 1.4%. The nanostructure-dendrite composites exhibit high yield strengths of 1525–1755 MPa together with large plastic strains of 4.7–6.0%. The as-arc melted samples exhibit relatively lower yield strengths of 1037–1073 MPa with very large plastic strains of 16.5–17.9% because of the coarser grain size of the matrix. The large plasticity of the composites is attributed to the retardation of localized shear banding and the excessive deformation in the nanostructured matrix due to the in situ formed dendrites. The deformation and the fracture mechanisms of the nanostructure-dendrite composites are discussed based on fractography observations.     

Effect of shock-wave loading on mechanical and thermomechanical characteristics of shape-memory alloys 45Ti–45Ni–10Nb and 43Ti–46Ni–8Nb–3Zr

This work was performed to study the behavior of 45Ti–45Ni–10Nb and 43Ti–46Ni–8Nb–3Zr (at %) shape-memory alloys (SMAs) under the effect of severe dynamic deformation to use the obtained results to develop technologies based on SMAs. Cast alloys were used for the tests. The elemental and phase compositions of the alloys in the initial state, as well as the phase composition, kinetics, and temperatures of phase transformations after heat treatment (annealing in a vacuum at 850°C for 4 h, furnace cooling) have been determined. The mechanical and thermomechanical characteristics of these alloys before and after shock-wave loading have been determined.     

Peculiarities of ball-milling induced crystalline–amorphous transformation in Cu–Zr–Al–Ni–Ti alloys

An amorphization process in (Cu₄₉Zr_45−xAl_6+x)_100−y−zNi_yTi_z (x = 1, y, z = 0; 5; 10) induced by ball-milling is reported in the present work. The aim was investigation of the effect of Ni and Ti addition to Cu₄₉Zr₄₅Al₆ and Cu₄₉Zr₄₄Al₇ based alloys as well as type of initial phases on the amorphization processes. Also the milling time sufficient for obtaining fully amorphous state was determined. The entire milling process lasted 25 h. Drastic structural changes were observed in each alloy after first 5 h of milling. In most cases, after 15 h of milling the powders had fully amorphous structure according to XRD except for those ones, where TEM revealed a few nanosized crystalline particles in the amorphous matrix. In (Cu₄₉Zr₄₅Al₆)₈₀Ni₁₀Ti₁₀ alloy the amorphization process took place after 12 h of milling and the amorphous state was stable up to 25 h of milling. In the case of (Cu₄₉Zr₄₄Al₇)₈₀Ni₁₀Ti₁₀ alloy the powders have fully amorphous structure between 12 h and 15 h of milling.     

Crystallization process and shape memory properties of Ti–Ni–Zr thin films

The crystallization process of as-deposited Ti–Ni–(10.8–29.5)Zr amorphous thin films was investigated. The Ti–Ni–Zr as-deposited films with a low Zr content exhibited a single exothermic peak due to the crystallization of (Ti,Zr)Ni with a B2 structure. In contrast, a two-step crystallization process was observed in the Ti–Ni–Zr thin films with a high Zr content. Shape memory behavior of Ti–Ni–Zr thin films heat treated at 873–1073 K was investigated by thermal cycling tests under various stresses. The martensitic transformation start temperature increased with increasing Zr content until reaching the maximum value, then decreased with further increasing Zr content. The inverse dependence of transformation temperature on Zr content in the thin films with a high Zr content is due to the formation of a NiZr phase during the crystallization heat treatment. The formation of the NiZr phase increased the critical stress for slip but decreased the recovery strain.     

The Oxidation Behaviour of Alloys Based on the Ni–Co–Al–Ti–Cr System

The isothermal oxidation behaviour of a series of quinary Ni–Co–Al–Ti–Cr alloys were studied at 800 °C. Alloys with higher Cr concentrations exhibited lower mass gain after 100-h exposure, as did the alloys richest in Ni and Al for a given Cr concentration. Extensive internal oxidation and nitridation was also observed in all alloys, except those containing the highest concentrations of Ni and Al. All alloys studied generated continuous chromium oxide layers, beneath which alumina particles were observed. Compositional analysis of the subscales identified shallower Cr concentration gradients in alloys containing equiatomic levels of Ni and Co, suggesting increased availability of Cr in the alloy. Thermodynamic calculations confirmed that these alloys contained higher concentrations of Cr in their γ matrices as a result of a combination of both the elemental partitioning behaviour and the increased mole fraction of γ′ precipitates forming in the alloy.     

Phase separation in Ni-rich Ni–Ti: the metastable states

The microstructure of Ni-11.3 at.% Ti single crystals was investigated after quenching from the solid solution at 1440 K and after ageing at 873 K for various periods of time by using transmission electron microscopy and X-ray scattering near fundamental reflections and superstructure reflections of the ordered precipitates. The two-stage decomposition sequence with the initial formation of metastable γ″ precipitates followed by metastable γ′ precipitates as found by small-angle neutron scattering is confirmed. The long-range order parameter of these precipitates is always close to the maximum value achievable at a given composition. The presence of the first metastable state (γ″) is related to a rearrangement of the precipitates on a macro-lattice in order to minimize the elastic energy due to coherency strains.