Effect of the deviation of the chemical composition from the stoichiometric composition on the structural and phase transformations and properties of rapidly quenched Ti50 + xNi25 ? xCu25 alloys

Methods of X-ray diffraction, transmission and scanning electron microscopy, and electron diffraction have been used to study phase composition and structure of an almost stoichiometric alloy Ti₅₀Ni₂₅Cu₂₅. The alloys of the quasi-binary section TiNi-TiCu to be studied, which exhibit in the initial ascast state thermoelastic martensitic transformations B2 ↔ B19 and related shape-memory effects, have been produced by rapid quenching of the melt (melt spinning technique). The chemical composition of the Ti_{50 + x} Ni_{25 − x} Cu₂₅ alloys was varied with respect to titanium and nickel within x ≤ ±1% (from Ti₄₉Ni₂₆Cu₂₅ to Ti₅₁Ni₂₄Cu₂₅). It has been shown that the rapid quenching from the melt at a cooling rate of 106 K/s provides amorphization for all the alloys under consideration. Heating to 723 K or higher temperatures leads to the devitrification of the amorphous alloys with the formation of a polycrystalline structure of the B2 austenite. The mechanical properties of the alloys have been measured in the initial amorphous state and after subsequent heat treatment. It has been established that, depending on the degree of deviation of the alloy from the stoichiometric composition, which leads to solid solution decomposition in the process of nanocrystallization upon heat treatment, there occur regular changes in the mechanical properties and shape-memory effects of the alloys. The characteristic temperatures of the onset and finish of the process of crystallization from the amorphous and amorphous-crystalline states and the critical temperatures of the onset and finish of the forward and reverse thermoelastic martensitic transitions have been determined by measuring temperature dependences of the electrical resistivity of the alloys. The diagram of the dependence of the critical temperatures on the chemical composition of the alloy has been constructed.     

Structure and phase transformations in copper-alloyed rapidly melt-quenched Ni<Subscript>50</Subscript>Ti<Subscript>32</Subscript>Hf<Subscript>18</Subscript>-based alloys with high-temperature shape memory effect

Methods of transmission and scanning electron microscopy, chemical microanalysis, electron diffraction, and X-ray diffraction have been used to carry out the comparative study of the structure and chemical and phase composition of thin ribbons of four quasi-binary alloys (Ni₅₀Ti₃₂Hf₁₈, Ni₄₅Ti₃₂Hf₁₈Cu₅, Ni₃₅Ti₃₂Hf₁₈Cu₁₅, and Ni25Ti32Hf18Cu25) obtained in the amorphous state by rapid quenching from the melt by jet spinning. The critical temperatures of the devitrification and B2 ? B19′ martensitic transformation of the alloys have been determined based on the data of temperature dependences of the electrical resistivity. The specific features of the formation of the ultrafine-grained structure upon the devitrification and of the phase transformations have been studied depending on the heat-treatment regimes and chemical composition of the alloys (concentration of copper atoms).     

The microstructure and properties of rapidly quenched Ti-rich Ti-Ni binary alloys with shape memory effects

The structure, phase composition, and martensitic transformations in binary titanium-rich Ti-Ni alloys with shape memory effects, produced by ultrarapid quenching using melt jet spinning, have been studied using electron microscopy, X-ray diffraction, and measurements of some physicomechanical properties in a wide temperature range. The alloys with a Ti content that exceeded the stoichiometric composition by 5% and more can be produced in an amorphous state. The alloys with a smaller deviation from the stoichiometry, as well as the Ti₅₀Ni₅₀ alloy, are crystallized in a submicrocrystalline state and undergo a B2 → B19’ martensitic transformation at temperatures above room temperature. They have high strength and plastic properties and demonstrate narrow-hysteresis shape-memory effects.     

Structural and phase transformations,mechanical properties,and shape-memory effects in quasibinary Ni<Subscript>50</Subscript>Ti<Subscript>38</Subscript>Hf<Subscript>12</Subscript> alloy obtained by quenching from the melt

Methods of transmission and scanning electron microscopy and chemical microanalysis, electron diffraction, and X-ray diffraction were used to systematically study the structure and the chemical and phase composition of the Ni₅₀Ti₃₈Hf₁₂ alloy synthesized by rapid quenching from the melt and subjected to various heat treatments. The critical temperatures of the devitrification of the initially amorphous rapidly quenched alloy and the B2 ? B19′ thermoelastic martensitic transformations have been determined. The lattice parameters of the B2 austenite and thermoelastic B19′ martensite have been measured. The main features of the formation of an ultrafine-grained structure in the alloy and the subsequent phase transformations (martensitic transformation and the decomposition with the formation of an intermetallic phase of the (Ti,Hf)₂Ni type) have been studied depending on the regimes of heat treatment. Based on the results of measurements of mechanical properties upon tension (σ_M, σ_u, and δ) and the shape-memory effects (degree of shape recovery depending on the deformation by bending; and magnitude of the reversible strain ε_rev), regimes for obtaining high-strength and plastic states of the alloy with a shape-memory effect have been established.     

Structure and phase transformations in TiNiFe ternary alloys subjected to plastic deformation by high-pressure torsion and subsequent heat treatment

The results of a complex study of ternary TiNiFe alloys with a low-temperature shape-memory effect subjected to megaplastic deformation by high-pressure torsion (HPT) with subsequent heat treatment are presented. Investigations have been performed using X-ray diffraction, transmission and scanning electron microscopy, and measurements of electrical properties. It has been established that, at moderate degrees of reduction, the plastic deformation in the Ti₅₀Ni₄₉Fe₁ alloy induces a B2 ? B19′ thermoelastic martensitic transformation and the formation of a developed banded dislocation and twin structure in the B19′ martensite; in the Ti₅₀Ni₄₇Fe₃ alloy, a mainly analogous dislocation substructure is formed, but in the B2 austenite. The megaplastic deformation by HPT at room temperature leads to the amorphization of the Ti50Ni49Fe1 alloy and to the high-angle nanofragmentation of the Ti50Ni47Fe3 alloy. Specific features of the evolution of the structure and martensitic transformations in the TiNiFe ternary alloys after plastic deformation and heat treatment have been established. It has been found that the heat treatment of both alloys after HPT at temperatures of 553–773 K results in the formation of a nanocrystalline or mixed nano-submicro-crystalline structure.     

Thermoelastic martensitic transformations,mechanical properties,and shape-memory effects in rapidly quenched Ni<Subscript>45</Subscript>Ti<Subscript>32</Subscript>Hf<Subscript>18</Subscript>Cu<Subscript>5</Subscript> alloy in the ultrafine-grained state

Methods of transmission and scanning electron microscopy and chemical microanalysis, electron diffraction, and X-ray diffraction were used to study the structure and the chemical and phase composition of ribbons of the four-component quasi-binary alloy Ni₄₅Ti₃₂Hf₁₈Cu₅. The influence of the synthesis regimes and subsequent heat treatment of the alloy on the formation of the amorphized state and ultrafine-grained structure has been determined. The critical temperatures of the devitrification and of the _B2 ? _B19' thermoelastic martensitic transformation have been established based on the data of the temperature dependences of the electrical resistivity. The lattice parameters of the _B2 and _B19' phases and the (Ti,Hf)₂Ni phase have been determined by X-ray diffraction. The mechanical properties of the alloy were determined in tensile tests, and the shape-memory effects in the ribbons of the alloy were measured using bending tests.     

Phase transformation and damping behavior of lightweight porous TiNiCu alloys fabricated by powder metallurgy process

Porous TiNiCu ternary shape memory alloys (SMAs) were successfully fabricated by powder metallurgy method. The microstructure, martensitic transformation behavior, damping performance and mechanical properties of the fabricated alloys were intensively studied. It is found that the apparent density of alloys decreases with increasing the Cu content, the porous Ti₅₀Ni₄₀Cu₁₀ alloy exhibits wide endothermic and exothermic peaks arisen from the hysteresis of martensitic transformations, while the porous Ti₅₀Ni₃₀Cu₂₀ alloy shows much stronger and narrower endothermic and exothermic peaks owing to the B2-B19 transformation taking place easily. Moreover, the porous Ti₅₀Ni₄₀Cu₁₀ alloy shows a lower shape recovery rate than the porous Ti₅₀Ni₅₀ alloy, while the porous Ti₅₀Ni₃₀Cu₂₀ alloy behaves reversely. In addition, the damping capacity (or internal friction, IF) of the porous TiNiCu alloys increases with increasing the Cu content. The porous Ti₅₀Ni₃₀Cu₂₀ alloy has very high equivalent internal friction, with the maximum equivalent internal friction value five times higher than that of the porous Ti₅₀Ni₅₀ alloy.     

Effect of heat treatment on structural and phase transformations in the Ti49.5Ni50.5 alloy amorphized by high-pressure torsion

Results are presented for a study of the structural and phase transformations that occur in the titanium-nickelide shape-memory alloy Ti_49.5Ni_50.5 subjected to heat treatment after deformation-induced amorphization by megaplastic high-pressure torsion (HPT) using five or ten revolutions of Bridgman anvils. The investigations were performed using transmission and scanning electron microscopy, X-ray diffraction, and measurements of the temperature dependences of electrical resistivity and magnetic susceptibility. It has been established that the crystallization of the alloy already occurs upon low-temperature treatment, beginning with ～500 K. The evolution of the structure and the stage character of the development of crystallization and recrystallization processes depending on temperature have been determined. It has been shown that the annealing of the amorphized alloy makes it possible to obtain highly homogeneous nanostructured, submicrocrystalline, or bimodal states in the B2 austenite. A complete diagram of thermoelastic martensitic transformations of the B2 austenite has been constructed in the region from a nanostructured to a conventional polycrystalline state (with a grain size of 20–50 μm). The effect of size on the stabilization of austenite has been revealed and its specific features have been studied for the B2 → R and B2(R) → B19′ martensitic transformations depending on the structural state of the alloy.     

Effect of heat treatment on the structure and properties of rapidly quenched binary titanium-enriched Ti-Ni alloys with a shape-memory effect

The effect of heat treatment on the structure, martensitic transformations, and properties of rapidly quenched binary titanium-enriched TiNi alloys with a shape-memory effect, which were produced by melt-spinning, has been studied using transmission and scanning electron microscopy, X-ray diffraction, and measurements of mechanical properties and electrical resistivity over a wide temperature range. Annealing of initial amorphous alloys was found to ensure their nanocrystallization with the formation of a two-phase (TiNi + Ti₂Ni) nanocomposite structure. The annealing of initial submicrocrystalline alloys initiates their decomposition with the heterogeneous formation of Ti₂Ni disperse particles in the supersaturated B2 austenite matrix. All alloys under study undergo a single B2 ? B19′ martensitic transition occurring above room temperature, exhibit high strength and plasticity, and demonstrate a narrow-hysteresis shape-memory effect.     

Formation of nanoscaled precipitates and their effects on the high-temperature shape-memory characteristics of a Ti50Ni15Pd25Cu10 alloy

The effects of thermomechanical treatment on the microstructure and high-temperature shape-memory characteristics of a TiNiPdCu alloy were investigated. An unexpected precipitation behavior was identified in a Ti₅₀Ni₁₅Pd₂₅Cu₁₀ alloy. Very high densities of nanoscale precipitates of TiPdCu and Ti₂Pd types were found to be formed in the thermomechanically treated Ti₅₀Ni₁₅Pd₂₅Cu₁₀ alloy. A spinodal type of decomposition process was expected to be the cause of the observed precipitation behavior. It was noticed that the preferential diffusion of Cu atoms towards the heterogeneous nucleation sites promoted the precipitation of TiPdCu-type precipitates, which in turn promoted the precipitation of fine Ti₂Pd-type precipitates. These precipitates greatly increased the resistance against the transformation-induced plasticity and creep deformation, especially at high stresses and high temperatures, mainly because of the high-temperature stability of these precipitates. High densities of these nanoscaled precipitates caused an anomalous increase in hardness and retarded the martensitic transformation. It was expected that the current research results could be highly beneficial for the development of high-temperature shape-memory alloys stable at temperatures >773 K, while keeping the benefits of ease of fabrication.     

Formation of the nanocrystalline structure in the Ti<Subscript>50</Subscript>Ni<Subscript>25</Subscript>Cu<Subscript>25</Subscript> shape-memory alloy under severe thermomechanical treatment

Results of comparative studies of the structure of the cast martensitic Ti₅₀Ni₂₅Cu₂₅ alloy in the initial state, after severe plastic deformation by high-pressure torsion (HPT), and after subsequent annealing are presented. The studies have been performed by X-ray diffraction, transmission and scanning electron microscopy, and measurements of electrical properties. It has been established that the alloy undergoes almost complete amorphization after torsion using 5 and 10 rev of anvils under a pressure of 7 GPa. This result can be explained by the large value of shear deformation (true strain from 6 to 7 units) and the retention of an extremely large quantity of highly dispersed (less than 3–4 nm in size) nanocrystals with a distorted B2 lattice in the amorphous matrix even at room temperature. Their determining role as nuclei of crystallization ensures the total process of low-temperature nanocrystallization upon subsequent annealing, beginning from 250–300°C. It is shown that the annealing of the alloy amorphized during HPT makes it possible to produce extremely uniform nanocrystalline (NC), submicrocrystalline (SMC), or bimodal (NC + SMC) structures of B2 austenite. For the first time, a complete diagram of thermoelastic martensitic transformations in the field of B2-austenite states, from nanostructured to usual polycrystalline, has been constructed for the Ti₅₀Ni₂₅Cu₂₅ alloy. The size effect of stabilization of the martensite transformation has been found in the nanocrystalline B2 alloy.     

Microstructure and superelastic properties of free forged Ti–Ni shape-memory alloy

Elemental titanium (Ti) and nickel (Ni) powders were consolidated by spark plasma sintering (SPS) to fabricate Ti–51%Ni (mole fraction) shape-memory alloys (SMAs). The objective of this study is to enhance the superelasticity of SPS produced Ti–Ni alloy using free forging as a secondary process. Products from two processes (with and without free forging) were compared in terms of microstructure, transformation temperature and superelasticity. The results showed that, free forging effectively improved the tensile and shape-memory properties. Ductility increased from 6.8% to 9.2% after forging. The maximum strain during superelasticity increased from 5% to 7.5% and the strain recovery rate increased from 72% to 92%. The microstructure of produced Ti–51%Ni SMA consists of the cubic austenite (B2) matrix, monoclinic martensite (B19′), secondary phases (Ti₃Ni₄, Ti₂Ni and TiNi₃) and oxides (Ti₄Ni₂O and Ti₃O₅). There was a shift towards higher temperatures in the martensitic transformation of free forged specimen (aged at 500 °C) due to the decrease in Ni content of B2 matrix. This is related to the presence of Ti₃Ni₄ precipitates, which were observed using transmission electron microscope (TEM). In conclusion, free forging could improve superelasticity and mechanical properties of Ti–51%Ni SMA.     

Magnetic-field-induced martensitic transformations in Ni47 − x Mn42 + x In11 alloys (with 0 ≤ x ≤ 2)

Magnetic properties and martensitic transformations in the Ni_{47 ? x} Mn_{42 + x} In₁₁ alloys (with 0 ≤ x ≤ 2) have been studied. The magnetic-field-induced martensitic transformation was found to be observed for all the alloys. The critical temperatures of magnetic and structural phase transformations, temperature dependences of spontaneous magnetization of austenite and martensite, and the critical field, at which the martensitic transformation occurs, have been determined based on magnetic measurements performed for the alloys under study. The spontaneous magnetization of the alloys in the martensitic state has been shown to be lower than that in the magnetic-field-induced austenitic state by a factor of six.     

Combined effects of work hardening and precipitation strengthening on the cyclic stability of TiNiPdCu-based high-temperature shape memory alloys

The combined effects of work hardening and precipitation strengthening were employed to improve the cyclic stability of TiNiPdCu-based high-temperature shape memory alloys. Annealing after cold deformation resulted in the formation of nano-scale TiPdCu and Ti₂Pd precipitates, stable at high temperatures in Ti₅₀Ni_25?xPd₂₅Cu_x alloys. The nano-scale precipitates were also observed to retard recovery/recrystallization processes at higher temperatures. It was found that the combined effects of work hardening and precipitation strengthening remarkably enhanced the high-temperature stability of the Ti₅₀Ni₂₀Pd₂₅Cu₅ alloy and increased its maximum working temperature range while keeping the transformation temperatures and recovery strains at sufficiently high levels. Precipitation strengthening helped to greatly improve the high-temperature cyclic stability of the alloy. Creep tests at 673 K under 500 MPa confirmed that the better high-temperature cyclic stability of the precipitate-containing alloy was mainly due to its higher creep resistance.     

Microstructure and high-temperature shape-memory effect in Ni54Mn25Ga21 alloy

1 Introduction Shape memory alloys (SMAs) have developed rapidly in the past few decades as new functional materials, with commercial applications in pipe couplings, medical implants, electrical connectors and various actuators etc[1?3]. But the highest …     

Formation of nanocrystalline structure in the amorphous Ti50Ni25Cu25 alloy upon severe thermomechanical treatment and the size effect of the thermoelastic martensitic B2 ? B19 transformation

The results of the comparative analysis of the Ti₅₀Ni₂₅Cu₂₅-alloy structures produced in the initial amorphous state by rapid quenching from the melt (RQM), after severe plastic deformation by torsion under high pressure (HPT), and postdeformation heat treatment (PHT) are presented. The study was carried out using neutron and X-ray diffraction, transmission and scanning electron microscopy, and measurements of electrical properties. The initially amorphous alloy has been established to nanocrystallize after torsion under a pressure of 7 GPa to 0.5 revolutions of the anvil. Then, after 1, 5, 10, and 15 rev, the alloy again undergoes the strain-induced amorphization even with the retention, even after 5–15 rev, of a large number of highly dispersed nanocrystals less than 3–4 nm in size with a distorted B2 lattice in the amorphous matrix. Their crucial role as nuclei of crystallization provides the total low-temperature nanocrystallization during subsequent annealing starting from 250–300°C. It is shown that PHT of the alloy amorphized by HPT makes it possible to produce extremely uniform nanocrystalline (NC), submicrocrystalline (SMC), or bimodal (NC + SMC) austenitic B2-type structures in it. A complete diagram of thermoelastic martensitic transformations in the region of B2-austenite states, from nanostructured state to conventional polycrystalline one, has been constructed. The size effect on the stabilization of martensitic transformation in nanocrystalline B2 alloy has been established.     

富镍镨掺杂镍钛形状记忆合金的微结构、相变特性与硬度

采用真空熔炼法向NiTi二元合金中掺杂Pr稀土元素,制备了多组分原子分数的Ni₅₀Ti_50-xPr_x（x=0,0.1,0.3,0.5,0.7,0.9）合金。研究了Pr元素的添加对NiTi合金金相组织、相变温度和硬度的影响。结果表明,Ni₅₀Ti_50-xPr_x合金由NiTi基体与NiPr夹杂相组成,其中Ni₅₀Ti_49.5Pr_0.5合金的马氏体相变温度达73 ℃,合金的热滞窄至37 ℃,维氏硬度约为2850 MPa。Pr元素的添加显著降低了NiTi合金的马氏体相变温度,同时,与其他NiTi基合金相比,NiTiPr合金保持了较窄的热滞和较高的硬度。     

Microstructure and martensitic transformation of cast TiNiSi shape memory alloys

The martensitic transformation behavior, second phases and hardness of Ti₅₁Ni_49−xSi_x shape memory alloys (SMAs) with x = 0, 1 and 2 at.% are investigated. The transformation temperature of one stage martensitic reaction B2 ↔ B19′ is associated with the forward (M_s) and reverse (A_s) martensitic transformations, respectively. All experimental DSC results such as martensitic transformation peaks (M*) and reverse martensitic transformation peaks (A*) are increased and became sharper with increasing Si-content. The microstructure investigation of the studied SMAs (Ti₅₁Ni_49−xSi_x) showed that there are two types of precipitated second phase particles. The first one is Ti₂Ni which mainly located at grain boundaries and intermetallic compound of Ti₂(Ni + Si) phase distributed inside the matrix. The volume fraction of these two phases is increased with Si content. Additionally, a small amount of Si remained in solid solution of the matrix of Ti₅₁Ni_49−xSi_x SMAs. Moreover, hardness of Ti₅₁Ni_49−xSi_x SMAs is increased as the Si-content increases.     

Influence of Ti additions on martensitic transformation and magnetic properties of cast Ni51Fe22−xGa27Tix shape memory alloys

The effect of Ti addition on the microstructure, martensitic transformation, magnetic and mechanical properties of polycrystalline Ni₅₁Fe_22?x Ga₂₇Ti _x (x=0, 2 and 4) ferromagnetic shape memory alloy was investigated by scanning electron microscope, differential scanning calorimetry and X-ray diffraction. The results showed that the martensitic transformation temperature increases monotonously with the increase of fraction of Ti substitution for Fe. The increase in the martensite transformation temperatures should be related to the change of the electron concentration after the addition of Ti to Ni₅₁Fe_22?x Ga₂₇Ti _x alloys. According to the results of X-ray diffraction and magnetic properties, Ti has significant effect the structure of Ni₅₁Fe_22-x Ga₂₇Ti _x . Adding of 4 at% Ti altered the structure of the matrix from five-layered tetragonal martensite of Ni₅₁Fe₂₂Ga₂₇ and Ni₅₁Fe₂₀Ga₂₇Ti₂ alloys to non-modulated tetragonal martensite. Magnetic properties proved that the alloy transits from ferromagnetic, five-layered tetragonal martensite, to paramagnetic, non-modulated martensite structure, with increasing Ti content to 4 at.%. Saturation magnetization, remnant magnetization and coercivity of the alloy were significantly influenced by Ti additions. Hardness values of Ni₅₁Fe₂₂Ga₂₇ increased by the addition of Ti.     

Martensitic transformations and magnetic-field-induced strains in Ni50Mn50−x Gax alloys

Concentration dependences of the temperatures of forward and reverse martensitic transformations in Ni₅₀Mn_50?x Ga_x alloys (x = 19–25) and features of the jumpwise elongation ε induced by magnetic field H in a single crystal of the Ni₅₀Mn_28.5Ga_21.5 alloy have been studied. A single-variant state of martensite in the single crystal was formed by compression under the action of both a reference magnetic field and mechanical loading. It has been shown that when employing uniaxial mechanical compression, several large jumps (whose nature is associated with the appearance of structural defects hindering the displacement of boundaries of martensite twins) arise in curves of the single-crystal elongation induced by an applied perpendicular magnetic field H _⊥.