Violation of the sequence of martensite crystals formation on cooling and their shrinking on heating during B2 ↔ B19′ martensitic transformation in Ti40.7Hf9.5Ni44.8Cu5 shape-memory alloy

An in situ transmission electron microscopy study of the B2 ? B19′ martensitic transformation in Ti_40.7Hf_9.5Ni_44.8Cu₅ shape memory alloy was carried out. It was observed that the sequence of the martensite crystals shrinking on heating differed from the sequence of the martensite crystal appearance on previous cooling. This was shown that strain nanodomain formation on cooling prior to the forward martensitic transformation resulted in accumulation of the elastic energy. This led to the dependences of the elastic energy stored on cooling or released on heating on the volume fraction of the martensite phase became different. In this case, at the same volume fraction of the martensite phase, the configuration of the martensite crystals on cooling and heating was different and it was a reason for a violation of the sequence of the martensite crystal formation on cooling and its shrinking on heating.     

Features of the surface layers of TiNi-based alloy thin ribbons

The chemical composition of the surface of TiNi-based alloys in the form of ribbons produced by rapid melt quenching in oxygen-containing environment has been investigated. It is shown that titanium oxide is formed on the Ti₅₀Ni₂₅Cu₂₅ alloy surface, while on the Ti_39.2Ni_24.8Cu₂₅Hf₁₁ alloy surface titanium and hafnium oxides are formed. Atomic-force microscope images reveal crystalline structures of titanium oxide with sizes of up to 500 × 500 nm² on the surface of the Ti₅₀Ni₂₅Cu₂₅ sample. After removing the surface oxide layer by ion etching, the ratio of elements becomes close to the stoichiometric composition.     

Tendency of metallic crystals to amorphization in the process of severe (Megaplastic) deformation

The main features of the transition of crystalline Ni₅₀Ti₃₀Hf₂₀, Ti₅₀Ni₂₅Cu₂₅, Zr₅₀Ni₁₈Ti₁₇Cu₁₅, and Fe₇₈B_8.5Si₉P_4.5 alloys with various tendencies to amorphization into an amorphous state upon melt quenching and in the course of severe deformation in Bridgman anvils have been considered. The crystalline state of these alloys has been produced using various methods of annealing. In the iron-based alloy, single-phase and two-phase crystalline states have been studied. The nickel- and titanium-based alloys after annealing were in a single-phase crystalline state; the zirconium-based alloy, in a two-phase state. It is shown that at the same degree of deformation the rates of amorphization of crystalline alloys differ substantially; namely, the single-phase crystalline titanium- and iron-based alloys amorphize easily, whereas the Zr-based alloy amorphizes only poorly, just like the two-phase iron-based alloy. It can be assumed that the tendency to deformation-induced amorphization of crystalline alloys and the corresponding crystalline phases is mainly determined by three factors: mechanical, thermodynamic, and concentration-related.     

Susceptibility of crystalline alloys to deformational amorphization during torsion under quasi-hydrostatic pressure

Features of the transition of Ni₅₀Ti₃₀Hf₂₀, Ti₅₀Ni₂₅, Zr₅₀Ni₁₈Ti₁₇Cu₁₅, and Fe₇₈B_8.5Si₉P_4.5 crystalline alloys with different susceptibilities to amorphization upon annealing and in the amorphous state during intense deformation in a Bridgman chamber are considered. The single- and two-phase crystalline states of the chosen alloys are obtained in different annealing modes. It is shown that the amorphizing rate of crystalline alloys differ substantially at the same degree of deformation; i.e., single-phase crystalline alloys based on titanium nickelide and iron amorphize well, while zirconium-based alloy amorphizes weakly in a manner similar to two-phase iron alloy. We believe that the LDA of crystalline alloys and their corresponding crystalline phases is determined by mechanical, thermodynamic, and concentration factors.     

Experimental valence-band study of Ti(NiCu) alloys with different compositions and crystal structures

The density of valence-band electronic states of Ti(NiCu) alloys with different crystal structures and elemental compositions has been studied by X-ray photoelectron spectroscopy. It has been established that the change in the crystal state initiated by a martensitic transformation or a transition from the amorphous state to the crystal state does not affect the valence-band electronic state density distribution of the Ti₅₀Ni₅₀ and Ti₅₀Ni₂₅Cu₂₅ alloys. It has been shown that a change in the elemental composition leads to a noticeable redistribution of the electronic density in alloys of the Ti₅₀Ni_{50 ? x} Cu _x system (x = 0, 10, 15, 25, 30, 38, 50 at. %). As the copper concentration in the Ti(NiCu) alloys increases, the contribution of the Ni d states in the vicinity of the Fermi level decreases, with the d band of nickel shifting toward higher binding energies, and that of copper, toward lower binding energies.     

High glass formability for Cu–Hf–Ti alloys with small additions of Y and Si

The effects of small substitutions of Si and Y on the glass-forming ability of a Cu₅₅Hf₂₅Ti₂₀ glassy alloy are reported and discussed. Fully glassy rods with diameters up to 7 and 6.5 mm were produced for Cu_54.5Hf₂₅Ti₂₀Si_0.5 and Cu_{55? x} Hf₂₅Ti₂₀Y_0.3 alloys, respectively. The addition of Si enlarged ΔT_x (= T_x ? T _g, where T _g and T_x are crystallisation and glass transition temperatures, respectively) considerably, from 25 to 53 K for the Cu₅₄Hf₂₅Ti₂₀Si₁ alloy. However, the results showed that the parameters obtained from thermal analysis, such as T _rg , ΔT_x and γ[= T_x /(T _g + T _l)] are not reliably correlated with the glass-forming ability (GFA), at least for these bulk glass-forming alloys. The scavenging effects of the Y and Si, in particular the possibility of Y reducing the oxides, could be responsible for enhancing the GFA. It is proposed that the effectiveness of small additions of Si in enhancing the GFA may be the result of the possible formation of HfSiO₄ having a very large negative enthalpy of formation and, as a strong network former, it would form glassy particles which would be ineffective as nucleating agents.     

In situ synchrotron X‐ray diffraction analysis of deformation behaviour in Ti–Ni‐based thin films

Deformation mechanisms of as‐deposited and post‐annealed Ti_50.2Ni_49.6, Ti_50.3Ni_46.2Cu_3.5 and Ti_48.5Ni_40.8Cu_7.5 thin films were investigated using the in situ synchrotron X‐ray diffraction technique. Results showed that initial crystalline phases determined the deformation mechanisms of all the films during tensile loading. For the films dominated by monoclinic martensites (B19′), tensile stress induced the detwinning of 〈011〉 type‐II twins and resulted in the preferred orientations of (002)_B19′ parallel to the loading direction (∥ LD) and (020)_B19′ perpendicular to the LD (⊥ LD). For the films dominated by austenite (B2), the austenite directly transformed into martensitic variants (B19′) with preferred orientations of (002)_B19′ ∥ LD and (020)_B19′ ⊥ LD. For the Ti_50.3Ni_46.2Cu_3.5 and Ti_48.1Ni_40.8Cu_7.5 films, martensitic transformation temperatures decreased apparently after post‐annealing because of the large thermal stress generated in the films due to the large differences in thermal expansion coefficients between the film and substrate.     

Nanocrystalline platinum layer deposited on NiTiCu shape memory strip

The Ni₂₅Ti₅₀Cu₂₅ shape memory strip was covered by thin nanocrystalline platinum layer. Structure of the layer was studied by means of X-ray diffraction and transmission electron microscopy. Transformation temperatures were determined using differential scanning calorymetry (DSC). The studies show that the layer reveals nanocrystalline structure with average crystalline size of 44 nm. Lattice distortion was relatively low –0.19%. Almost 25% of total grains are oriented along 〈111〉 direction. It was stated that the nanocrystalline platinum layer does not limit martensitic transformation in the covered strip, which reveals one step reversible martensitic transformation from the parent B2 phase to the orthorhombic martensite B19 phase. Also no influence of the layers on the shape recovery was noticed.     

Shape memory behaviour of annealed Ti48.5Ni(51.5− x )Cu x (x = 6.2–33.5) thin films

The shape memory behaviour of (Ni,Cu)-rich Ti–Ni–Cu thin films (Ti_48.9Ni_44.9Cu_6.2, Ti_48.5Ni₄₀Cu_11.5, Ti_48.6Ni_35.9Cu_15.5, Ti_48.3Ni_28.4Cu_23.3, Ti_48.3Ni_23.9Cu_27.8 and Ti_48.5Ni₁₈Cu_33.5) annealed at 773, 873 and 973 K for 1 h was investigated. The films with 6.2, 11.5–15.5 and 23.3–33.5 at% Cu showed a single-stage deformation due to a B2 ? B19′ transformation, a two-stage deformation due to the B2 ? B19 ? B19′ transformation and a single-stage deformation due to the B2 ? B19′ transformation, respectively. The martensitic transformation start temperature (M _s) increased with increasing Cu content and then levelled off for more than 15 at% Cu, indicating a high Ms temperature of 345 K. Temperature hystereses were almost 15 K for all films with more than 10 at% Cu. The critical stress for slip increased with increasing Cu content and increased significantly for the Ti_48.5Ni₁₈Cu_33.5 film, whereas the maximum recoverable strain significantly decreased for the Ti_48.5Ni₁₈Cu_33.5 film. With decreasing annealing temperature, the critical stress for slip increased, but the M _s temperature decreased. It was found that films with 11.5 at% Cu or more, annealed at 873 K, showed a high martensitic transformation temperature and a high critical stress for slip.     

Grain oriented NiMnSn and NiMnIn Heusler alloys ribbons produced by melt spinning: Martensitic transformation and magnetic properties

We outline the microstructural, martensitic transformation and magnetic properties of Heusler alloys with starting compositions Ni₅₀Mn₃₇Sn₁₃, Ni₅₀Mn₃₆In₁₄, and Mn₅₀Ni₄₀In₁₀, produced by melt spinning. The ribbons were obtained in argon environment at a high wheel linear speed of 48 m s⁻¹ (typical dimensions: 1.2-2.0 mm in width, 4-12 mm in length, and 7-12 μm in thickness). EDS microanalysis showed that the resulting average elemental chemical composition is slightly shifted with respect to the starting one. Ribbons are fully crystalline and tend to show a highly ordered columnar-like microstructure with grains running through the entire ribbon thickness; the larger dimension of the grains is perpendicular to the ribbon plane. As-spun alloys were single-phase with ferromagnetic bcc L2₁ austenite as high-temperature parent phase. At low temperatures austenite transforms into a structurally modulated martensite with a lattice symmetry that depends on the system (7 M orthorhombic for Ni₅₀Mn₃₇Sn₁₃, 10 M monoclinic for Ni₅₀Mn₃₆In₁₄, and 14 M monoclinic for Mn₅₀Ni₄₀In₁₀). Magnetization isotherms measured in the temperature interval where martensite thermally transforms into austenite confirmed the occurrence of field-induced reverse martensitic transition in the alloys studied.     

Crystallization behaviour in a new multicomponent Ti16.6Zr16.6Hf16.6Ni20Cu20Al10 metallic glass developed by the equiatomic substitution technique

A new amorphous Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ alloy has been developed using the novel equiatomic substitution technique. Melt spinning Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ forms an amorphous phase with a large supercooled liquid region, ΔT=70°C. After isothermal annealing within the supercooled liquid region for 3 h at 470°C, the amorphous alloy crystallizes to form a fine-scale distribution of 2–5 nm nanocrystals, and the supercooled liquid region increases to ΔT=108°C. Atomic-scale compositional analysis of this partially crystalline material using a three-dimensional atom probe (3DAP) is unable to detect any compositional difference between the nanocrystals and the remaining amorphous phase. After annealing for 1 hr at 620°C, the amorphous alloy crystallizes to form 20–50nm equiaxed grains of a hexagonal-type C14 Laves phase with lattice parameters a = 5.2Å and c = 9.0 Å. 3DAP analysis shows that this Laves phase has a composition very close to that of the initial amorphous phase, suggesting that the alloy crystallizes via a polymorphic rather than a primary crystallization mechanism, despite the complexity of the alloy composition.     

Microstructure and shape memory behaviour of annealed Ti51.5Ni(48.5- x )Cu x ( x = 6.5–20.9) thin films

Ti-rich Ti–Ni–Cu amorphous films (Ti_51.9Ni_41.6Cu_6.5, Ti_51.6Ni_36.8Cu_11.6, Ti_51.5Ni_33.1Cu_15.4 and Ti_51.7Ni_27.4Cu_20.9), formed by sputtering, were annealed at 773, 873 and 973?K for 1?h and their structures and shape memory behaviours investigated. All the films annealed at 773?K for 1?h exhibited Guinier–Preston (GP) zones, but these precipitates were absent after annealing at 873?K or higher. Instead of GP zones, coherent plate precipitates of a Ti₂Cu phase were formed in films annealed at 873?K for 1?h, when the Cu content was between 11.6 to 20.9 at.%. The strain–temperature curves under constant stresses of Ti_51.6Ni_36.8Cu_11.6 and Ti_51.5Ni_33.1Cu_15.4 films showed a two-step deformation associated with the B2???B19???B19′ transformation, whereas Ti_51.9Ni_41.6Cu_6.5 and Ti_51.7Ni_27.4Cu_20.9 films showed a single-step deformation associated with the B2?B19′ and B2?B19 transformations, respectively. The two kinds of plate precipitates, GP zones and a Ti₂Cu phase were found to be effective to increase the critical stress for plastic strain.     

Thermal evolution of short-range order in Cu–Hf-based amorphous alloys

A Perturbed Angular Correlation study on melt-spun Cu₆₀Hf₂₀Ti₂₀ and Cu₆₀Hf₄₀ is presented. The influence of Ti addition on thermal stability and crystallization mechanism is followed by differential scanning calorimetry. The evolution of quadrupole parameters with measurement temperature is analyzed in both alloys in order to get insight into the crystallization process. Although an intricate crystallization mechanism is observed for the Ti containing alloy, the final stage is similar, irrespective of minority atom.     

Formation of long-period nanostructural phases in Ni<Subscript>2</Subscript>MnGa-based <Emphasis Type="Italic">L</Emphasis>2<Subscript>1</Subscript> alloys with thermoelastic martensitic transitions

The crystalline structures of martensite phases in Ni₂MnGa-based ternary alloys have been studied in a wide range of temperatures and compositions transmission and scanning electron microscopy, X-ray diffraction, and electron diffraction. It is found that long-period nanostructural phases with thin-plate morphology are formed as a result of martensitic transformation in Ni₂MnGa-based alloys.     

Crystallization of amorphous Hf100−xCux alloys

The crystallization of Hf_100−xCu_x (x=33,44,50,59) amorphous alloys was studied by the TDPAC technique. The different stages in the transformation towards equilibrium were investigated through the evolution of the quadrupole perturbation after thermal annealings. The crystallization kinetics of Hf₆₇Cu₃₃ and Hf₅₆Cu₄₄ was analyzed using the Johnson-Mehl-Avrami equation. General trends in the crystallization behavior are discussed.     

Effect of Mn incorporation for Ni on the properties of melt spun off-stoichiometric compositions of NiMnGa alloys

The investigation addresses the effect of Mn incorporation for Ni on the properties of a series of Ni_77−xMn_xGa₂₃ (x=22-29; at%) ferromagnetic shape memory alloys prepared in the form of ribbons by a melt spinning technique. Phase transformation studies in these ribbons by differential scanning calorimetry revealed that austenitic start and martensitic start temperatures decreased with the increase in Mn content. The Curie temperature (T_C) of these alloys determined from thermal variation of magnetisations was found to rise with increasing Mn content. The martensitic transformation temperatures were above T_C in low Mn containing (x=22 and 23) alloys. Morphology observed through transmission electron microscopy manifested complex martensitic features in the alloy with x=22 while x=29 had an austenitic phase. The alloys with intermediate Mn content (x=24, 25) had overlapping magnetic and martensitic transformations close to room temperature. The thermal lag between austenitic and martensitic characteristic temperatures in these alloys has been corroborated to their structural state. X-ray diffraction indicated a predominant martensite phase and austenite phase in low and high Mn containing alloys respectively. In-situ diffraction studies during thermal cycle indicate martensite-austenite transformations.     

Amorphous Heusler alloys: The effect of annealing on structure and magnetic and transport properties

Alloys with the Heusler compositions Cu₂MnIn, Cu₂MnAl and Cu₂MnSn have been prepared as amorphous films for the first time. The structural disorder results in as-deposited films which are not ferromagnetic and, in fact, exhibit spin-glass properties due to the distribution of MnMn distances and co-existence of positive and negative exchange interactions. Annealing of the In and Al alloys can restore single phase ordered Heusler structures which are ferromagnets with Curie temperatures typical of bulk alloys. The calculated Mn moments remain lower than the bulk values of 4 μ_B probably due to disorder at grain boundaries. Films annealed under non-optimum conditions crystallized into several non-magnetic structures as well as the magnetic L2₁ Heusler phase. Lattice constants of all phases were determined. The temperature dependence of resistivity through the amorphous-crystalline transformation was found to confirm the results of thermal annealing on structure and magnetization.     

Formation of nanostructured states in ternary TiNiFe-based shape memory alloys during megaplastic deformation and subsequent heat treatment

The ternary metastable TiNiFe alloys that exhibit a low-temperature shape memory effect and are subjected to plastic deformation by rolling or high-pressure torsion followed by heat treatment are studied by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and electrical resistivity measurements. It is found that moderate plastic deformation of a Ti₅₀Ni₄₉Fe₁ alloy at room temperature initiates the thermoelastic B2 ? B19’ martensitic transformation and the formation of a developed banded dislocation and twin substructure in the B19’ martensite. This deformation of a Ti₅₀Ni₄₇Fe₃ alloy forms a similar dislocation substructure but in B2 austenite. Megaplastic deformation by high-pressure torsion causes amorphization in the Ti₅₀Ni₄₉Fe₁ alloy and nanofragmentation in the Ti₅₀Ni₄₇Fe₃ alloy. The evolution of the nanostructure and the martensitic transformations in TiNiFe-based ternary alloys is studied during plastic deformation and subsequent annealing at various temperatures.     

Effect of alloying on the structure and phase transformations in Ni-Mn alloys alloyed by titanium

The crystal structure of NiMn alloy alloyed by titanium in a wide range of temperatures and compositions has been investigated using resistivity measurements, transmission electron microscopy, electron diffraction, and X ray diffraction. It is found that alloying by titanium not only decreases the martensitic transformation temperature but also changes the martensite crystal structure. The martensitic transformation temperatures are determined and the diagram of martensitic transformations for Ni₅₀Mn_{50 ? x} Ti _x alloys is constructed.     

Shape memory effect in Ti-Ni-Cu alloy caused by Joule heating

The properties of melt-spun Ti₅₀Ni₂₅Cu₂₅ alloy have been investigated by multiple thermocycling (up to 8000 cycles) within the martensitic transformation temperature range under constant mechanical stress from 5 to 200MPa, using electric current heating. A nearly linear relation is established between the alloy strain and electric resistance, which is independent of the applied stress and the number of thermal cycles.