Influence of Sc addition on microstructure and transformation behaviour of Ni24.7Ti50.3Pd25.0 high temperature shape memory alloy

Vacuum-arc melted Ni_24.7Ti_50.3Pd_25.0 and Ni_24.7Ti_49.3Pd_25.0Sc_1.0 (at.%) alloys were investigated to study effect of Sc micro-addition on microstructure and transformation behaviour of NiTiPd alloy. Study showed that microstructure of homogenized NiTiPd alloy consisted of NiTiPd matrix interspersed with Ti₂(Ni,Pd) precipitates. In contrast, NiTiPdSc alloy showed a single phase NiTiPdSc matrix with a few scandium oxide particles at isolated places. TEM and X-ray diffraction studies confirmed matrix phase of the alloys to be of orthorhombic B19 structure. TEM observations showed that NiTiPdSc alloy had relatively larger martensite plates with a smaller twin ratio compared to that of NiTiPd alloy. Also, APB (anti-phase boundary) like regions with twinless martensites was observed in both the alloys, area fraction of APB-like regions being more in NiTiPdSc alloy. Thermal analysis showed that transformation temperatures (TTs) of NiTiPd alloy decreased significantly with addition of Sc. The martensite finish temperature (M_f) of 181 °C for NiTiPd alloy lowered to 139 °C upon 1.0 at.% Sc addition. The transformation hysteresis of Ni_24.7Ti_49.3Pd_25.0Sc_1.0 (at.%) alloy was measured to be 7 °C, significantly lower than that of 15 °C for Ni_24.5Ti_50.0Pd_25.0Sc_0.5 alloy, reported in literature. Alloy purity, lower volume fraction of second phase and presence of twinless/small twin ratio martensite in microstructure is believed to be the reasons for such low transformation hysteresis. The transformation behaviour of the alloys upon stress-free thermal cycling was found stable, variation in TTs being within 1–2 °C.     

Evolution and stability of phases in a high temperature shape memory alloy Ni49.4Ti38.6Hf12

Ni_49.4Ti_38.6Hf₁₂ shape memory alloy has been characterized for structure, microstructure and transformation temperatures. The microstructure of the as-cast sample consists of B19′ and R-phases, and (Ti,Hf)₂Ni precipitate phase along the grain boundaries in the form of dendrites. The microstructure of the solution treated sample contains only B19′ martensite phase, whereas a second heat treatment after solutionizing results in reappearance of the R-phase and the (Ti,Hf)₂Ni grain boundary precipitate phase in the microstructure. A detailed microstructural examination shows the presence of precipitates having both coherent and incoherent interface with the matrix, the type of interface being dictated by the crystallographic orientation of the matrix phase. The present study shows that the (Ti,Hf)₂Ni precipitates having coherent interface with the matrix, drive the formation of the R-phase in the microstructure.     

Comparative study of R-phase martensitic transformations in TiNi-based shape memory alloys induced by point defects and precipitates

We studied the influence of point defects (Fe) and precipitates (Ti₃Ni₄) on the characteristics of R-phase martensitic transformation by comparing the transport and thermal properties of as-quenched Ti₅₀Ni₄₆Fe₄ and annealed Ti_48.7Ni_51.3 shape memory alloys. Both alloys undergo a weak first-order R-phase transformation with a small thermal hysteresis (less than 7 K) and non-zero transformation strain, suggesting the introduction of point defects and precipitates lead to a stable R-phase in these alloys due to the defects induced local lattice deformations. Furthermore, our study revealed that the transition temperature, transformation width, and transformation strain of the investigated R-phase TiNi-based alloys are strongly affected by the induced defects. As a result, the annealed Ti_48.7Ni_51.3 has a higher transition temperature than that of Ti₅₀Ni₄₆Fe₄, as expected.     

The effect of aging on the B2-R transformation behaviors in Ti-51at%Ni alloy

Aging is an effective way to control the transformation behaviors of Ti–Ni shape memory alloys. In the present study, the transformation behaviors of Ti-51at%Ni polycrystals after aging at various temperatures (250 °C–500 °C) for different time were investigated by DSC measurement. It is found that B2-R transformation temperature (R_S) of the aged samples is uniquely determined by the aging temperature for aging above 400 °C, being almost independent on aging time. Higher aging temperature causes a lowering of R_S temperature. At lower aging temperatures (e.g., 250 °C, 300 °C), R_S gradually increases with aging time and finally saturates. The saturated R_S value is also a unique function of the aging temperature. These facts can be explained by the phase equilibrium between Ti–Ni matrix (B2) and Ti₃Ni₄ precipitates. The Ti₃Ni₄ precipitates formed at different aging temperatures alter the Ni concentration in B2 matrix and consequently cause an aging temperature dependence of the R-phase transformation of B2 matrix. By considering the kinetics of precipitation reaction, the “time-independence” of R_S for high temperature aging and the “time-dependence” of R_S for low temperature aging can also be reasonably understood. Besides, the R–B19′ transformation temperature (M_S) gradually increases with aging time as well, which can also be understood by considering the growth of precipitates during aging.     

Co对Ti-Ni形状记忆合金相变和形变特性的影响

用热重分析仪、X射线衍射仪、示差扫描量热仪及拉伸试验研究了Co对Ti-49.8Ni(at%,下同)形状记忆合金相变和形变特性的影响。结果表明,中温退火态Ti-49.8Ni合金冷却/加热时的相变类型为A→R→M/M→A(A—母相,R—R相,M—马氏体相);随退火温度升高,该合金的马氏体相变温度升高,R相变温度先升高后降低;该合金室温相组成为马氏体,具有形状记忆效应(SME)。用1%Co置换等量Ti后所得Ti-49.8Ni-1Co合金冷却/加热时的相变类型为A→R→M/M→R→A,相变温度低,室温组成相为母相A,具有超弹性(SE)特性。退火温度低于600℃时,Ti-Ni基合金的SME和SE特性良好,退火温度超过600℃后,合金氧化加剧,SME和SE特性变差,塑性显著提高。     

Multi-stage transformation in annealed Ni-rich Ti49Ni41Cu10 shape memory alloy

Multi-stage transformation (MST) in 500 °C annealed Ni-rich Ti₄₉Ni₄₁Cu₁₀ shape memory alloy (SMA) is investigated by differential scanning calorimetry (DSC), dynamic mechanical analyzer (DMA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The as solution-treated alloy undergoes B2 ↔ B19 ↔ B19′ two-stage transformations. Ti(Ni,Cu)₂ precipitates are formed in 500 °C annealed specimens. Alloy annealed at 500 °C for 6–24 h exhibits MST. This MST is confirmed by DMA tests and is composed of B2₁ ↔ B19₁ ↔ B19′₁ and B2₂ ↔ B19₂ ↔ B19′₂ transformations corresponding to the regions near and far from Ti(Ni,Cu)₂ precipitates, respectively. Experimental results show that the more the annealing time, the more the B2₁ ↔ B19₁ ↔ B19′₁ transformations and finally only B2₁ ↔ B19₁ ↔ B19′₁ transformations retain with the transformation temperatures close to those of Ti₅₀Ni₄₀Cu₁₀ SMA.     

R-phase formation in Ti39Ni45Cu16 shape memory thin films and bulk alloys discovered by combinatorial methods

The combinatorial fabrication and high-throughput characterization of a Ti–Ni–Cu shape memory thin film composition spread led to the discovery of the shape memory alloy Ti₃₉Ni₄₅Cu₁₆, which exhibits a single B2 → R-phase transformation above 25 °C with a thermal hysteresis width <1 K. Here we show that the thin film results correctly predict the phase transformation behavior of bulk material upon cooling from the high temperature phase. For both thin film and bulk, a two-step B2 → R-phase → B19′ transformation was found. The B2 → R-phase transformation can be exploited independently, due to a significant temperature separation of the two transformation steps. The shape memory effect in both thin film and bulk samples is limited due to the two-phase microstructure. Transmission electron microscopy investigations revealed the existence of Ti(Ni,Cu)₂ precipitates within the TiNi(Cu) matrix, which are concluded to be responsible for the R-phase formation and separation of the transformation steps.     

In situ TEM observation of two-step martensitic transformation in aged NiTi shape memory alloy

Martensitic transformation was investigated in an aged NiTi alloy with DSC and a temperature controllable TEM specimen stage to observe the influence of Ti₁₁Ni₁₄ precipitates and R-phase on martensitic transformation in situ. The R-phase, conventional martensitic twins, and a new morphology of interwoven austenite/martensitic structure were observed.     

Microstructure and shape memory behavior of Ti55.5Ni44.5−xCux (x = 11.8–23.5) thin films

The microstructure and shape memory behavior of Ti_55.5Ni_45.5−xCu_x (x = 11.8–23.5) thin films annealed at 773, 873, and 973 K for 1 h were investigated. None of the films except the Ti_55.4Ni_32.8Cu_11.8 film annealed at 773 K for 1 h had any precipitates in the B2 grain interiors and their grain sizes were small (less than 1 μm). Increasing the annealing temperature caused grain growth and thus a decrease in the critical stress for slip and an increase in the martensitic transformation start temperature (Ms). The grain size was also controlled by the growth of a second phase. In the three-phase equilibrium region of Ti₂Ni, Ti₂Cu and TiNi, Ti₂Cu grains grew faster than Ti₂Ni grains, leading to a decrease in the critical stress for slip and an increase in the Ms temperature with increasing Cu content.     

Crystallization behavior in severely cold-drawn Ti50Ni47Fe3 wire

The microstructures and crystallization behavior of Ti–47 at% Ni–3 at% Fe shape memory alloy wire under the condition of severe cold drawing at room temperature and different post-deformation annealing processes were intensively investigated using transmission electron microscope(TEM) and differential scanning calorimetry(DSC). It is indicated that the amorphous phase is dominant in the Ti50Ni47Fe3 wire after the cold drawing of 78 % areal reduction. The critical temperature for recrystalization is determined at about 300 °C. The average grain size grows from 7 up to 125 nm when annealing temperature rises from300 to 500 °C. Post-deformation annealing process exerts significant influence on the crystallization temperature which climbs up with the increase of annealing temperature.     

V含量对等原子比NiTi形状记忆合金微观组织、相变行为和显微硬度的影响

采用光学显微镜、扫描电子显微镜、X射线衍射仪、差示扫描量热仪和显微硬度计等测试手段,研究了V含量对等原子比NiTi形状记忆合金微观组织、相变行为和显微硬度的影响规律。结果表明：当V含量为0.5at%时,具有等轴晶组织的NiTiV形状记忆合金包含B19'' 和 Ti₂Ni相;当V 含量大于0.5at%时,NiTiV形状记忆合金形成B19''相、Ti₂Ni相和V的富集相,并且随着V含量增加,V的富集相越来越多聚集于晶界。进一步分析表明,Ni_49.75Ti_49.75V_0.5和Ni_49.25Ti_49.25V_1.5 形状记忆合金发生了B2?B19''的一级相变,而Ni_48.75Ti_48.75V_2.5和Ni_48.25Ti_48.25V_3.5形状记忆合金发生了B2?R?B19''的二级相变,尽管降温过程中同时发生了部分的R相变与B19''马氏体相变。随着V含量增加,相变温度随着V含量增加逐渐降低,其主要原因是Ni/Ti比例的增加。此外,随着V含量增加,合金的显微硬度值呈现先降低然后几乎保持不变的变化规律。     

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.     

Effect of Ni4Ti3 precipitation on martensitic transformation in Ti–Ni

Precipitation of Ni₄Ti₃ plays a critical role in determining the martensitic transformation path and temperature in Ni–Ti shape memory alloys. In this study, the equilibrium shape of a coherent Ni₄Ti₃ precipitate and the concentration and stress fields around it are determined quantitatively using the phase field method. Most recent experimental data on lattice parameters, elastic constants, precipitate–matrix orientation relationship and thermodynamic database are used as model inputs. The effects of the concentration and stress fields on subsequent martensitic transformations are analyzed through interaction energy between a nucleating martensitic particle and the existing microstructure. Results indicate that R-phase formation prior to B19′ phase could be attributed to both direct elastic interaction and stress-induced spatial variation in concentration near Ni₄Ti₃ precipitates. The preferred nucleation sites for the R-phase are close to the broad side of the lenticular-shaped Ni₄Ti₃ precipitates, where tension normal to the habit plane is highest, and Ni concentration is lowest.     

Effect of precipitation on the shape memory effect of Ti50Ni25Cu25 melt-spun ribbon

The present research aims to provide accurate understanding of the relation between precipitation (volume fraction, morphology, type) and shape memory effect of Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbon. Rapid thermal annealing was used to control the microstructural development while the shape memory effect of the ribbon was determined under constraint thermal cycling. The results show that the precipitation process takes the following sequence: B11 TiCu → B11 TiCu + Ti₂(Ni, Cu) → Ti₂(Ni, Cu) with increasing annealing temperature or duration. The shape memory effect is found to depend on both the volume fraction and the distribution of the precipitates. The former affects the shape recovery strain through reduction of the transformation volume participating the shape recovery. The latter affects the shape recovery strain through strengthening the matrix thus reducing the martensite strain which is more predominant under low constraint stresses. Precipitation strengthening, on the other hand, reduces the tendency of dislocation generation/movement, thus reducing the irreversible strain and improving shape recovery strain. This understanding provides guidelines on the optimization of the shape memory properties of the Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbon via post-processing annealing.     

Microstructure and martensitic transformation of TiNiNbB shape memory alloys

In present work, microstructure, martensitic transformation and mechanical properties of Ti₄₄Ni_47−xNb₉B_x (x = 0, 0.5, 1, 5 at.%) alloys were investigated as a function of B content. The results show that the addition of B significantly influences the microstructure of the alloys. The microstructure of Ti₄₄Ni₄₇Nb₉ alloy consists of B2 parent phase matrix and β-Nb phase. When the B content is 0.5 at.%, Nb₃B₂ phase presents. With further increasing B content to above 1 at.%, TiB and NbB phases present instead of Nb₃B₂ phase. With increasing B content, the transformation temperatures increase due to the reduced Ni/Ti ratio and Nb content in the matrix. The mechanical properties can be optimized by the addition of 1 at.% B.     

Structure of martensite in Ti-rich Ti–Ni–Cu thin films annealed at different temperatures

After annealing at different temperatures, there are different types of precipitates in Ti-rich Ti–Ni–Cu thin films: plate-like Guinier–Preston (GP) zones, Ti₂Cu precipitates and spherical Ti₂Ni precipitates. The (0 1 1) compound twins and (1 1 1) type I twins are dominant in Ti-rich Ti–Ni–Cu thin films annealed at different temperatures, which suggests that the precipitates do not change the twinning modes of the B19 martensite. However, the amount of the (0 1 1) compound twin increases with increasing annealing temperature due to its small twinning shear. In thin films with GP zones or Ti₂Ni precipitates, the amount of martensite with a single-pair morphology is less than that in thin films without precipitates. And in thin film with Ti₂Cu + Ti₂Ni precipitates, hardly any martensite with a single-pair morphology is observed. For the different types of precipitates at the different annealing temperatures, the obstacle of the precipitates to the growth of the B19 martensite plate also varies. The GP zones slightly hinder the growth in the width of martensite, resulting in wavy twin boundaries at the martensite variant tip. The Ti₂Cu precipitates can change both the width and the direction of the martensite plates. Ti₂Ni precipitates also significantly disturb or impede the growth of the martensite variants. These effects lead to a decrease in the maximum shape recoverable strain with increasing annealing temperature.     

Phase transformations in a Ti50Ni47.5Fe2.5 shape memory alloy

An optical metallographic study involving surface relief was made of the phase transformations in a Ti₅₀Ni_47.5Fe_2.5 alloy. The formation and reversion of two different kinds of surface relief associated with R-phase and martensitic transformations were observed upon thermal cycling. The nature of the R-phase transition and its microstructural changes during deformation were also observed; these are described.     

Effect of ageing on transformation kinetics and internal friction of Ni-rich Ni–Ti alloys

In Ni-rich Ni–Ti alloys the ageing treatments create finely dispersed Ti₃Ni₄ precipitates in the B2-based matrix. Formed precipitates are known to influence the phase transformation temperatures and to facilitate the R-phase transformation. In addition to the change in the phase transformation behaviour, the ageing treatments are also reported to affect internal friction and mechanical properties of Ni–Ti alloys.In the present work, by means of systematic DSC and DMA studies the effects of the ageing treatments on the phase transformation as well as on the internal friction and mechanical properties of Ni-rich Ni–Ti alloy were studied. As an extension to earlier studies, the present study concentrates both on the effects of the ageing time and the ageing temperature systematically. By combining the results of the DSC measurements of phase transformation behaviour to the DMA measurements of internal friction and mechanical behaviour of the Ni-rich Ni–Ti alloy, the present study gives yet unpublished information about the comprehensive effects of the ageing treatments on these alloys. These results enable to control the phase transformation temperatures, internal friction and mechanical properties of the Ni-rich Ni–Ti alloy by selecting the suitable ageing treatment.Results showed that the noticed effects of the ageing treatments on mechanical properties could be explained with the changes in the size, distribution, density and coherency of the formed Ti₃Ni₄ precipitates. The high internal friction values can be explained as the contribution of the internal stress fields and increased amount of mobile interfaces as the result of the formed Ti₃Ni₄ precipitates. The amount of mobile interfaces seems to be more dominant factor for the increased internal friction value than the effect of the internal stress fields. Therefore, the optimal internal friction values can be obtained with a proper aging treatment which will yield a high density of small Ti₃Ni₄ precipitates.     

Thermal and transport properties of as-grown Ni-rich TiNi shape memory alloys

Electrical resistivity, Seebeck coefficient, specific heat and thermal conductivity measurements on the Ti_50−xNi_50+x (x = 0.0–1.6 at.%) shape memory alloys are performed to investigate their thermal and transport properties. In this study, anomalous features are observed in both cooling and heating cycles in all measured physical properties of the slightly Ni-rich TiNi alloys (x ≤ 1.0), corresponds to the transformation between the B19′ martensite and B2 austenite phases. Besides, the transition temperature is found to decrease gradually with increasing Ni content, and the driving force for the transition is also found to diminish slowly with the addition of excess Ni, as revealed by specific heat measurements. While the signature of martensitic transformation vanishes for the Ni-rich TiNi alloys with x ≥ 1.3, the characteristics of strain glass transition start to appear. The Seebeck coefficients of these TiNi alloys were found to be positive, suggesting the hole-type carriers dominate the thermoelectric transport. From the high-temperature Seebeck coefficients, the estimated value of Fermi energy ranges from ∼1.5 eV (Ti_48.4Ni_51.6) to ∼2.1 eV (Ti₅₀Ni₅₀), indicating the metallic nature of these alloys. In addition, the thermal conductivity of the slightly Ni-rich TiNi alloys with x ≤ 1.0 shows a distinct anomalous feature at the B19′ → B2 transition, likely due to the variation in lattice thermal conductivity.     

Influence of aging on microstructure,martensitic transformation and mechanical properties of NiTiRe shape memory alloy

Aging is an effective way to adapt the microstructure, phase transformation and consequently the mechanical properties of NiTi shape memory alloys. In the present study, Ni₅₂Ti_47.7Re_0.3 shape memory alloy was solution treated at 1000 °C for 24 h then aged at various temperatures of 300, 400, 500 and 600 °C for 3 h. The influence of aging treatment on microstructure, martensitic transformation and mechanical properties of Ni₅₂Ti_47.7Re_0.3 was investigated. The microstructure of the solution treated alloy was martensite as a matrix phase and precipitates of Ti₂Ni phase. The aged alloys had a microstructure as same as that of solution treated alloy in addition to the existence of other types of precipitates like Ni₄Ti₃ and Ni₃Ti. The martensitic — austenitic transformation during heating and cooling was going through one stage of transformation. The martensitic phase transformation temperature increased by the increase of aging temperature but still lower than that of solution treated alloy.