Influence of high-energy impact actions on the elastic and anelastic properties of martensitic Cu–Al–Ni crystals

The influence of high-energy impact shock-wave loading on the microplasticity and macroscopic performance of the Cu–Al–Ni crystals in the β₁′ martensitic phase has been studied. Elastic and anelastic properties of quenched and aged polyvariant single crystals before and after impact shock-wave loading were measured in the temperature range 80–300 K, at a frequency of about 100 kHz in the strain amplitude-independent and amplitude-dependent ranges by means of the composite oscillator technique, and in the MHz frequency range using the pulse–echo technique. High-velocity impact loading of the specimens was realised by plane shock-waves with stress pulses with a duration of 2·10⁻⁶ s and stress amplitudes up to 5 GPa. A pronounced influence of impact shock-wave loading on the elastic and anelastic properties of the β₁′ martensite has been observed. A strongly marked softening of the material and an enhancement of damping properties are revealed up to the highest stress pulse amplitudes. This behaviour differs fundamentally from the one observed in ‘ordinary’ fcc metals. Changes of the defect structure induced by shock-wave loading, which may be responsible for the observed phenomena, have been discussed.     

Stabilisation of martensite by applying compressive stress in Cu-Al-Ni single crystals

Compression tests have been carried out for a Cu-Al-Ni single crystal at temperatures well above the martensitic transformation, near the transformation or below it (in martensitic state). The composition was selected in order to obtain either β-β′ or β-γ′ thermal martensitic transformations, after suitable thermal treatments. The characteristics of the martensitic transformation and structural changes after the compression tests have been studied by means of calorimetry (DSC) and TEM. The obtained results show that when a compressive stress is applied on quenched samples (TTA treatment, β-β′ thermal transformation) a β-(β′)-γ′ transformation or a β′-γ′ one are stress-induced, depending whether the initial state is the parent or the martensitic phase. For aged samples (TTB treatment, β-γ′ thermal transformation) the application of stress brings about the β-γ′ transformation or γ′ re-orientation, depending on the initial state. In all the cases a notable martensite stabilisation is observed only when the stress–strain loop is not closed, that means when a permanent strain remains in the material after unloading. A direct relationship between the applied deformation when stressing the sample and the degree of stabilisation has been obtained for different strain values (between 5% and 12%) and for each set of samples (TTA and TTB). At the same time, the evolution of the characteristics of the martensitic phases with the degree of deformation has been studied. The stress induced stabilisation mechanism is related to the presence of non-twinned γ′ martensite which makes difficult the retransformation to the parent phase.     

Towards understanding anelasticity of the β1′ martensitic phase of Cu–Al–Ni

The present work continues the series of experimental investigations undertaken in order to elucidate the mechanisms controlling elastic and anelastic properties of the β₁′ martensitic phase of Cu-based shape memory alloys. The paper reports an attempt to distinguish between ‘dislocation’ and ‘interface’ mechanisms of the internal friction in the β₁′ martensitic phase of Cu–Al–Ni single crystals. Two types of experiments have been performed. First, the ultrasonic strain amplitude-independent and amplitude-dependent internal friction (ADIF) of a monovariant specimen for temperatures 90–300 K is carefully re-examined. Second, in situ measurements of the ADIF and of the influence of ultrasonic oscillations on the plastic deformation (acoustoplastic effect) were carried out during quasistatic deformation of a quenched polyvariant specimen. Experimental results support a dislocation rather than an interface mechanism of anelasticity, at least at ultrasonic frequencies and moderate strain amplitudes.     

Structural anelasticity of NiTi during two-stage martensitic transformation

The two-staged thermoelastic martensitic transformation (TMT) B2→R→B19′ in polycrystalline equiatomic NiTi has been studied by means of measurements of strain amplitude-independent and amplitude-dependent internal friction (ADIF), Young’s modulus and amplitude-dependent modulus defects. The internal friction measurements were performed at a frequency of about 100 kHz, rendering negligible the transient internal friction component and allowing one to investigate the structural internal friction, much less dependent on the external parameters such as the heating/cooling rate or the frequency of vibrations. Attention is focussed on the amplitude-dependent anelasticity. Based on the data obtained, the anelasticity is associated with the dislocations inside the martensitic variants, not with the interfaces or interface dislocations, as is traditionally done. The ADIF and anelastic strain in the R phase have been found to be an order of magnitude higher than in the B19′ martensitic phase. This observation is explained by a much higher density of the dislocations inside the variants of the R phase as compared with that of the B19′ phase.     

Multi-stage martensitic transformations induced by repeated thermal cycling of equiatomic TiNi alloy

Usually a multi-stage martensitic transformation is observed in Ni-rich TiNi alloys after heat treatment at 350–500 °C. It is due to the internal stresses created by the Ni₄Ti₃ participate. In the present work it was found that the multi-stage martensitic transformation appeared in Ti–50.0 at.% Ni alloy after thermal cycles through the temperature range of the phase transitions. Annealed sample undergoing one-stage phase transition was subjected to 32 thermal cycles in the DSC apparatus. The results had shown that three-stage forward martensitic transformation observed after 32 thermal cycle was due to the B2 → R, B2 → B19′ and R → B19′ phase transitions. It was found that the B19′ phase obtained from the B2 phase underwent the reverse transformation at higher temperatures than the B19′ phase obtained from the R phase. After annealing the cycled sample at 400 °C the transformation behavior was similar to the non-thermal cycled alloy. It was concluded that the main reason for the multi-stage phase transition induced by the thermal cycles was the phase hardening.     

Cu content and annealing temperature dependence of martensitic transformation of Ti36Ni49−xHf15Cux melt spun ribbons

The martensitic transformation in Ti₃₆Ni_49−xHf₁₅Cu_x (x = 1, 3, 5, 8) ribbons has been investigated. Only B2 to B19′ transformation was detected in all the present ribbons. The martensitic transformation temperatures do not change obviously with increase in the Cu content except that they decrease when the Cu content is 3 at.%. The lattice parameters of B19′ martensite, a and c increase, b almost remains constant, while the monoclinic angle β decreases with increase in the Cu content. For the ribbons with Cu content of 1 and 3 at.%, the martensitic transformation temperatures change slightly when the annealing temperature increases. For the ribbons with Cu content of 5 and 8 at.%, with increase in the annealing temperature, the martensitic transformation temperatures almost do not change and then decrease rapidly when the annealing temperature is higher than 873 K. TEM observation shows that the microstructure of the ribbons with Cu content of 1 and 3 at.% contains the martensite matrix and the (Ti,Hf)₂Ni particles with the size of about 150 nm, which does not change obviously when the annealing temperature increases. This results in that the martensitic transformation temperatures are not sensitive to the annealing temperature in the ribbons with 1 and 3 at.% Cu content. However, nano-scale (Ti,Hf)₂Ni particles precipitate in the ribbons with Cu content of 5 and 8 at.% when the annealing temperature is 773 and 873 K, and then the (Ti,Hf)₂Ni particles grow and coarsen rapidly with further increase in the annealing temperature. The coarsening of the (Ti,Hf)₂Ni particles should be responsible for the dramatic decrease of the martensitic transformation when the annealing temperature is higher than 873 K. For all the present ribbons, the substructure of B19′ martensite is (001) compound twins, and the inter-variant relationship is mainly (011) type I twinning.     

Pre-martensitic phenomena in Ti40.7Hf9.5Ni44.8Cu5 shape memory alloy

Pre-martensitic phenomena such as abnormal resistivity growth, diffusion scattering, “tweed” contrast and internal friction peak were observed in Ti_40.7Hf_9.5Ni_44.8Cu₅ alloy prior to the forward martensitic transformation on cooling. It was shown that all the observed phenomena were due to the formation of quasi-static strain nanodomains in the B2 phase prior to the forward martensitic transformation. This led to accumulation of the elastic energy before the phase transition and resulted in the variation in thermodynamic balance for the forward martensitic transformation and, as a result, influenced the parameters of the phase transition. The appearance of elastic energy prior to the forward transformation caused a decrease in the forward and reverse martensitic transformations' start temperatures, a widening of the temperature range of the reverse transformation and an increase in the hysteresis of the transformation.     

Structure and anelasticity of Fe3Ge alloy

The structure and anelastic properties of Fe-27 at.%Ge alloy are studied. Long-term annealing of the as-cast alloy at 1273 K leads to homogenising and several transformations take place below 873 K. These low temperature transitions are studied by several methods: X-ray diffraction, calorimetry, vibrating-sample magnetometry and internal friction, and are related to magnetic transitions in the different phases. A high stability of the hexagonal (D0₁₉) phase at room temperature is recorded. The hexagonal β (B8₁) phase is also detected in the alloy at room temperature, while the presence of the ′ and phases is doubtful. A broad internal friction relaxation peak with the relaxation strength of Δ = 0.0036, the activation energy of about 1.78 eV and the preexponential relaxation time of τ₀ = 2 × 10⁻¹⁷ s was discovered and classified as the Zener peak in both the and β phases.     

Investigation of the martensitic transformation and the damping behavior of a superelastic Ti–Ta–Nb alloy

In this study the α″ stress-induced martensitic transformation and damping behaviour of the superelastic β-Ti–25Ta–25Nb alloy are investigated by tensile tests at room temperature and by dynamic mechanical analysis (DMA) in tensile mode for different applied stresses. Tensile tests show a fully non-linear elastic domain and, consequently, a specific method is proposed to determine the elastic modulus. Due to the wide range of temperature over which the martensitic transformation occurs in this class of alloys, the martensitic start temperature, M_s, is not a relevant parameter to characterize the transformation and the temperature M_max corresponding to the temperature of maximum transformation is used. The important gap between these two temperatures explains the fully non-linear elastic behaviour of this alloy during conventional tensile tests. It is observed that two main damping sources occur in this alloy: friction at austenite/martensite interfaces during the martensitic transformation and friction at martensite/martensite interfaces at lower temperature. However, a third unexpected damping peak is also observed at high stress. Its origin is discussed with respect to the orientation of the applied stress and with regard to the most favourably oriented martensite variants determined by Schmid factor analysis.     

Influence of annealing on magnetic field-induced structural transformation and magnetocaloric effect in Ni–Mn–In–Co ribbons

A study of the magnetic field-induced martensitic transformation and magnetocaloric effect in Ni₄₅Mn₃₇In₁₃Co₅ and Ni₄₆Mn₃₅In₁₄Co₅ ribbons prepared by melt-spinning was carried out. Annealing significantly increases the degree of ordering in the austenite phase, reduces the critical field and hysteresis of the magnetically induced martensitic transformation and increases the magnetically induced shift of martensitic transformation temperatures. For the most In-rich sample, Ni₄₆Mn₃₅In₁₄Co₅, annealing at 900 °C for 2 h leads to the formation of Co-rich face-centered cubic γ precipitates. The Curie temperature of the γ phase is about 370 K. The formation of the second phase has little impact on the hysteresis, but broadens the transformation interval and reduces the magnetic entropy change.     

Phase transformation and microstructural changes during ageing process of an Ag–Pd–Cu–Au alloy

Age-hardening behaviour and the related phase transformation and microstructural changes during isothermal ageing process were studied to elucidate the age-hardening mechanism of an Ag-based dental casting alloy composed of Ag–Pd–Cu–Au–Zn, Ir and In by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and energy dispersive spectroscopic microanalysis (EDS). In the hardness test at 350 and 400 °C, the hardness of the solution-treated specimen began to increase and reached a maximum value with increasing ageing time, and subsequently the hardness decreased gradually. By considering XRD results and SEM observations together, the solution-treated specimen consisted of three phases, the Ag-rich α₁ phase as a matrix, the Cu–Pd α₂ phase and the CuPd β phase with a CsCl-type as particle-like structures. By ageing the solution-treated specimen, the Ag-rich α₁ and Cu–Pd α₂ phases were transformed into the Ag-rich α^′₁ and Cu₃Pd α^′₂ phases, respectively. The CuPd β phase with a CsCl-type was not changed apparently during the ageing process. From the results of the hardness test, XRD study, SEM observations and EDS analysis, it could be derived that the hardness increased by the diffusion and precipitation of the Cu-rich phase from the Ag-rich matrix during the early stage of phase transformation of α₁ into α^′₁ and that the progress of coarsening of the Cu-rich precipitates with an entanglement structure caused the hardness decrease during the later stage of phase transformation of α₁ into α^′₁. The particle-like structures composed of the Cu–Pd α₂ and the CuPd β phase with a CsCl-type contributed little to the hardness increase which occurred in the early stage of aging process.     

Eutectoid transformations accompanied by ordering

Eutectoid transformations accompanied by ordering, unlike ordinary ones, proceed through non-pearlitic modes of transformations. Eutectoid invariants are classified into two categories in binary systems. The eutectoid invariant of A3()→D0₁₉(₂) + L1₀(γ) in the Ti-Al binary system belongs to the first category, in which one product phase has an ordered structure of a parent phase. Its transformation product exhibits a γ/₂ lamellar structure consisting of nearly perfectly aligned alternate lamellae of γ and ₂, which is formed by precipitation of γ plates in either or ₂ matrix with the Blackburn orientation relationship. The eutectoid invariant of A1(γ)→D0₂₂(γ″) + L1₂(γ′) in the Ni₃V-Ni₃Al pseudo-binary system is an example of the second category, in which both product phases have different ordered structures of a parent phase. The transformation of a 75Ni-18V-7Al alloy results in a ‘checkerboard’ pattern consisting of a periodic array of columns of γ′ and two γ″ orientation variants, which are formed by phase separation simultaneous with ordering.     

Microstructural changes produced by plastic deformation in the UNS S31803 duplex stainless steel

Plastic deformation by cold rolling produces important changes on microstructure of the duplex stainless steel UNS S31803. Structure refinement and martensitic transformation were detected and analyzed by microscopy, X-ray diffraction and magnetic measurements. True deformations in the range of 0.92–3.38 were applied. The maximum amount of ′ martensite was 30.2% obtained with the maximum deformation applied (3.38). The annealing at 400 °C promotes a further increase of ′ martensite content, as observed before in austenitic metastable steels. Hardness against deformation curves of AISI 304L and duplex steel were compared and analyzed. The stability of the martensite phase with temperature was investigated by magnetic measurements, and it is found that the reverse reaction ′ → γ starts between 500 and 520 °C.     

Control of microstructure and orientation distribution in Ni–Al-based (β/γ′) two phase alloys by thermomechanical processing

Microstructure and orientation distribution of two phase Ni–Al(β)/Ni₃Al(γ′) alloys obtained by thermomechanical processing were examined using electron back-scatter diffraction pattern technique. Cylindrical specimens were hot-compressed in the β phase region and subsequently annealed in the (β/γ′) two phase region. After the hot deformation, equiaxed β grains surrounded by high angle boundaries were homogeneously formed due to dynamic recrystallisation under adequate condition. Moreover, strong 1 1 1 fibre texture parallel to the compressive axis developed in the β phase because of the lattice rotation during hot deformation. After annealing in the two phase region, γ′ phase transformed from β phase with 1 1 1_β fibre texture satisfying the Kurdjumov–Sachs relationship and resulting in the formation of 1 1 0_γ′ fibre texture. Film-shaped γ′ phase preferentially often precipitated along the β grain boundaries and a large number of (β/γ′) boundaries were partially coherent. This thermomechanical processing was effective in controlling the crystallography of γ′ along the β grain boundaries.     

Effect of temperature,strain rate and grain size on the mechanical response of Ti3SiC2 in tension

Tensile, relaxation and cycling loading–unloading tests indicate that the mechanical response of Ti₃SiC₂ has a strong dependence on temperature and strain rate, but a weak dependence on grain size. Loading at low temperatures, and/or high strain rates, results in elastic and anelastic deformation, followed by brittle fracture. Anelastic deformation in this regime can be attributed to the easy glide of dislocation into pileups during loading, and their run back during unloading. At high temperatures (≈1100–1200°C), and/or low (<10⁻⁵ s⁻¹) strain rates, the response is plastic. The resulting strain is elastic, anelastic and plastic. Even at 1200°C, intense stress-relaxation processes are observed, and a sizable fraction (≈13%) of the strain is anelastic. At intermediate temperatures and strain rates (transition regime) the mechanical response is controlled by simultaneous damage formation (microcracking) and localized plastic deformation. Combining the results obtained in this work with previous results, viz. tensile creep and strain transient dip tests, a deformation map that takes into account temperature, grain size and strain rate is defined.     

Thermomechanical and martensitic transformation stresses of NiTiJSi thin film composites

The thermomechanical properties of Ni₅₀Ti₅₀ deposited on Si substrates was studied focusing on the thermoelastic stress, martensitic transformation stress and interaction of the film and substrate. Ni₅₀Ti₅₀/SiO₂/Si film composites display a two-way shape memory effect without training. The stresses giving rise to this effect are the thermoelastic stress evolving upon cooling from the temperature at which the amorphous as-deposited Ni₅₀Ti₅₀ was crystallized and martensitic transformation stress. It is shown how the thermoelastic bending can be compensated for in a (crystalline Ni₅₀Ti₅₀)/SiO₂/Si/(amorphous Ni₅₀Ti₅₀) trimorph. The experimentally determined temperature dependence of the stress outside the transformation region agrees with the calculated value of the thermoelastic stress; in the vicinity of the Ms and Af temperatures, which are equal to each other, it also agrees with the theoretical prediction based on the equilibrium thermodynamics of the sum of the film, substrate and film/substrate elastic (interaction) energies. The film/substrate interaction energy is derived from martensitic transformation characteristics through interface accommodation and mechanical constraints exerted by the substrate stiffness. This knowledge has been applied to fabricate a two way shape memory micro composite switch.     

Microstructure evolution in CoNiGa shape memory alloys

Magnetic shape memory CoNiGa alloys hold great promise as new smart materials due to the good ductility and a wide range of martensitic transformation (MT) temperatures as well as magnetic transition points. This paper reports the results of investigations on the equilibrium phase constitution and microstructure evolution in quenched or aged CoNiGa alloys using the optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) methods. The dendritic γ phase decreases as lowering of Ga content in studied two series of samples (Co₅₀Ni_50 − xGa_x, x = 0–50 and Co_100 − 2yNi_yGa_y, y = 15–35). Some γ′ precipitates with different morphologies were found in given alloys conducted with water quenching (WQ) at 800 °C or long-time ageing at 300 °C. After 800 °C quenching, the γ′ phase has a rod-like shape for the Co₅₀Ni₃₀Ga₂₀ alloy but shows a Widmanstätten morphology as Ga increases to 25 at%, and trends to be block structure in further high Ga content alloy. In the case of 300 °C aged alloys, the γ′ particles prefer to nucleate in interior of γ phase or at the interface of β–γ. We also presented an illustrative vertical section phase diagram keeping 50 at% Co, and isothermal section phase diagram at 1150 and 800 °C of the CoNiGa system. Based on the schematic ternary phase diagram, the composition scope which potentially holds over the magnetic pure martensite phase structure at room temperature (RT) was pointed out. It is believed that this optimized range alloys would play an important role in the functional materials design for application.     

Stress-induced martensitic transformation in Fe–Ni bicrystals

The effect of applied stress on martensitic transformation behaviour near the grain boundary was examined using Fe–32 at.% Ni bicrystals containing a 90°2 1 1 tilt or a 90°{2 1 1} twist grain boundary focusing on the martensite-start stress (σ_M), the morphology of martensites and the variant selection. The σ_M for single crystals and tilt boundary bicrystals increases almost linearly with increasing temperature (T), and the σ_M−T relation for tilt boundary bicrystals is situated in the higher temperature side than that for single crystals. In contrast, the σ_M of the twist boundary bicrystals exists between the correlated σ_M−T relations for single crystals and tilt boundary bicrystals. The variant selection near the tilt boundary is not sensitive to applied stress; some variants with the habit plane almost parallel to the boundary were symmetrically formed similar to those in the thermal transformation. The effect of loading axis to grain boundary on the martensitic transformation behaviour was also investigated.     

Martensitic transformation and anomalies in resistivity of (Ti–50Ni)1−xCx (x = 0.1, 0.5 at.%) shape memory alloys

Phase transformation of solid solution (Ti–50Ni)_1−xC_x (x = 0.1, 0.5 at.%) alloys have been studied by using differential scanning calorimetry, physical property measurement system and optical microscope. The transformation temperature decreases due to the existence of titanium carbide (TiC) particles compared with that of near-equiatomic Ti–Ni shape memory alloy. The resistivity vs. temperature curves show hysteresis. Thermoelastic martensitic transformation occurred in two alloys despite the difference in TiC content. Nevertheless, the resistivity results show different martensitic transformation routes. A one-step B2 → B19′ transformation occurred in the low TiC content alloy and an R transformation appeared in another alloy, suggesting that the martensitic transformation routes depended on the TiC content. The cumulative effect of the TiC particles causes the local stress field and lattice distortion to restrain the transformation of the B19′. On the other hand, the TiC content has an effect on the temperature coefficient of electrical resistivity (TCR) of alloys. The Ti–Ni–0.5C alloy shows a negative TCR in the range 100–300 K during which transformation occurs. Another alloy shows the opposite result. The cause of the negative TCR is briefly discussed.