Effect of solution treatment on the microstructure,phase transformation behavior and functional properties of NiTiNb ternary shape memory alloys fabricated via laser powder bed fusion in-situ alloying

Post-heat treatment is commonly employed to improve the microstructural homogeneity and enhance the mechanical performances of the additively manufactured metallic materials.In this work,a ternary(NiTi)91Nb9(at.%)shape memory alloy was produced by laser powder bed fusion(L-PBF)using pre-alloyed NiTi and elemental Nb powders.The effect of solution treatment on the microstructure,phase transformation behavior and mechanical/functional performances was investigated.The in-situ alloyed(NiTi)91Nb9 alloy exhibits a submicron cellular-dendritic structure surrounding the supersaturated B2-NiTi matrix.Upon high-temperature(1273 K)solution treatment,Nb-rich precipitates were precipitated from the supersaturated matrix.The fragmentation and spheroidization of the NiTi/Nb eutectics occurred during solution treatment,leading to a morphological transition from mesh-like into rod-like and sphere-like.Coarsening of theβ-Nb phases occurred with increasing holding time.The martensite transformation temperature increases after solution treatment,mainly attributed to:(i)reduced lattice distortion due to the Nb expulsion from the supersaturated B2-NiTi,and(ii)the Ti expulsion from theβ-Nb phases that lowers the ratio Ni/Ti in the B2-NiTi matrix,which resulted from the microstructure changes from non-equilibrium to equilibrium state.The thermal hysteresis of the solutionized alloys is around 145 K after 20%pre-deformation,which is comparable to the conventional NiTiNb alloys.A short-term solution treatment(i.e.at 1273 K for 30 min)enhances the ductility and strength of the as-printed specimen,with the increase of fracture stress from(613±19)MPa to(781±20)MPa and the increase of fracture strain from(7.6±0.1)%to(9.5±0.4)%.Both the as-printed and solutionized samples exhibit good tensile shape memory effects with recovery rates>90%.This work suggests that post-process heat treatment is essential to optimize the microstructure and improve the mechanical performances of the L-PBF in-situ alloyed parts.

Machine learning-assisted efficient design of Cu-based shape memory alloy with specific phase transition temperature

The martensitic transformation temperature is the basis for the application of shape memory alloys(SMAs),and the ability to quickly and accurately predict the transformation temperature of SMAs has very important practical significance.In this work,machine learning(ML)methods were utilized to accelerate the search for shape memory alloys with targeted properties(phase transition temperature).A group of component data was selected to design shape memory alloys using reverse design method from numerous unexplored data.Component modeling and feature modeling were used to predict the phase transition temperature of the shape memory alloys.The experimental results of the shape memory alloys were obtained to verify the effectiveness of the support vector regression(SVR)model.The results show that the machine learning model can obtain target materials more efficiently and pertinently,and realize the accurate and rapid design of shape memory alloys with specific target phase transition temperature.On this basis,the relationship between phase transition temperature and material descriptors is analyzed,and it is proved that the key factors affecting the phase transition temperature of shape memory alloys are based on the strength of the bond energy between atoms.This work provides new ideas for the controllable design and performance optimization of Cu-based shape memory alloys.

Laser powder bed fusion additive manufacturing of NiTi shape memory alloys: a review

NiTi alloys have drawn significant attentions in biomedical and aerospace fields due to their unique shape memory effect(SME),superelasticity(SE),damping characteristics,high corrosion resistance,and good biocompatibility.Because of the unsatisfying processabilities and manufacturing requirements of complex NiTi components,additive manufacturing technology,especially laser powder bed fusion(LPBF),is appropriate for fabricating NiTi products.This paper comprehensively summarizes recent research on the NiTi alloys fabricated by LPBF,including printability,microstructural characteristics,phase transformation behaviors,lattice structures,and applications.Process parameters and microstructural features mainly influence the printability of LPBF-processed NiTi alloys.The phase transformation behaviors between austenite and martensite phases,phase transformation temperatures,and an overview of the influencing factors are summarized in this paper.This paper provides a comprehensive review of the mechanical properties with unique strain-stress responses,which comprise tensile mechanical properties,thermomechanical properties(e.g.critical stress to induce martensitic transformation,thermo-recoverable strain,and SE strain),damping properties and hardness.Moreover,several common structures(e.g.a negative Poisson’s ratio structure and a diamond-like structure)are considered,and the corresponding studies are summarized.It illustrates the various fields of application,including biological scaffolds,shock absorbers,and driving devices.In the end,the paper concludes with the main achievements from the recent studies and puts forward the limitations and development tendencies in the future.

Effects of second phases on mechanical properties and martensitic transformations of ECAPed TiNi and Ti-Mo based shape memory alloys

TiNi and Ti-based shape memory alloys were processed by equal channel angular pressing （ECAP） at 673-773 K along Bc route to obtain ultrafine grains for increasing the strength of parent phase and improving the functional properties. The effects of both thermodynamically stable and metastable second phases on the mechanical properties and martensitic transformations of these alloys were investigated. It is found that thermodynamically stable Ti2Ni phase has no effect on martensitic transformation and superelasticity of Ti-rich TiNi alloy, thermodynamically stable α phase is harmful for ductility of Ti-Mo-Nb-V-Al alloy, but metastable Ti3Ni4 phase is effective for R phase transformation, martensitic transformation and superelasticity of Ni-rich TiNi alloy. The mechanisms of the second phases on the martensitic transformations and mechanical properties were discussed.

Microstructure,mechanical and shape memory properties of Ti-55Ta-xSi biomedical alloys

The effects of Si addition on microstructures, mechanical and shape memory properties of Ti-55Ta biomedical alloy were investigated. The results show that the microstructures consist of mainly α′′ martensite and a little β phase, and the grain size decreases obviously with increasing Si addition. When x = 0.2, small （Ti, Ta）3Si precipitates are formed at grain boundaries. With further increasing Si content, the amount of the precipitates gradually increases. The tensile and yield strength of Ti-55Ta-xSi alloys gradually increase with increasing Si addition, whereas elongation decreases. Ti-55Ta-0.1Si alloy exhibits the lowest elastic modulus and the best shape memory recoverable strain. It is revealed that the refinement of grain and the precipitation of （Ti, Ta）3Si phase are responsible to the changes of their mechanical and shape memory properties.

Effect of Sn substitution and heat treatment on microstructure and microhardness of Co_(38)Ni_(34)Al_(28-x)Sn_x magnetic shape memory alloys

Sn was used to replace Al in Co38Ni34Al28 alloy. The microstructure and microhardness of Co38Ni34Al28-xSnx （x=0, 1, 2, 3） magnetic shape memory alloys were investigated at different heat treatment temperatures （1373 K, 1473 K, and 1573 K） for 2 h. The results show that more Sn substitution reduces the content of γ-phase and a partial phase of martensite can be obtained in Co38Ni34Al28-xSnx （x=1, 2, 3） alloys after treatment at 1573 K for 2 h. The maximum martensite phase appears when 2% Al is substituted by Sn. The reverse martensitic transformation temperature of Co38Ni34Al28-xSnx alloys increases at x=1 and 2, then decreases as x=3. As the content of Sn and the temperature increase, the microhardness will increase.

Modeling of Ni_4Ti_3 precipitation during stress-free and stress-assisted aging of bi-crystalline NiTi shape memory alloys

The phase field method was applied to study the microstructure evolution of Ni4Ti3 precipitates during stress-free and stress-assisted aging of bi-crystalline NiTi shape memory alloys （SAMs） with two different initial Ni-contents of 51.5% and 52.5% （mole fraction）, respectively. The simulation results show that, during stress-free aging of the NiTi alloy with a low supersaturation of Ni （i.e., Ti-51.5%Ni）, the Ni4Ti3 precipitates exhibit a heterogeneous distribution with a high number density of particles at the grain boundary, leaving most of the grain interiors free of precipitates; while for the NiTi alloy with a high supersaturation of Ni （i.e., Ti-52.5%Ni）, the Ni4Ti3 precipitates show a homogeneous distribution across the entire simulation system. The stress-assisted aging can give rise to homogeneous distribution of the precipitates, regardless of the initial Ni-content; however, the distribution of variant type within the two grains is heterogeneous.

Effect of Co substitution on magnetic properties of Ni-Mn-Sn magnetic shape memory alloys

The effect of Co substitution on magnetic properties of Ni-Mn-Sn shape memory alloy was revealed by first-principles calculations. Large magnetization difference in Ni-Mn-Sn alloy obtained by addition of Co arises from enhancement of magnetization of austenite due to change of Mn-Mn interaction from anti-ferromagnetism to ferromagnetism. Total energy difference between paramagnetic and ferromagnetic austenite plays an important role in magnetic transition of Ni-Co-Mn-Sn. The altered Mn 3d states due to Co substitution give rise to difference in magnetic properties.

Effects of Co and Al addition on martensitic transformation and microstructure in ZrCu-based shape memory alloys

The effect of ternary alloying element Al and quaternary alloying element Co on the martensitic transformation of ZrCu-based shape memory alloy was investigated. The results show that the addition of Al and Co in ZrCu alloy decreases both the martensitic transformation temperature and the martensitic transformation temperature hysteresis. Transmission electron microscope (TEM) observations reveal that theCm martensite structure is the preferential formation phase. The intervariant structures in ZrCuAlCo alloy are (021) type I twins, while the dominant substructures inside the martensite variant are the (001) compound twins. With the increase of Co content, tensile fracture strength and strain are improved obviously.

Role of thermal martensite in shape memory effect of CoAl and CoNi alloys

To address the role of the HCP martensite in CoAl and CoNi shape memory alloys, the relationship between the shape memory effect （SME） and the content of the thermal and stress-induced HCP martensite was investigated in the solution-treated CoAl and CoNi alloys. In-situ optical observations were employed to investigate the contents of thermal HCP martensite before and after deep cooling and its influence on the stress-induced HCP martensite transformation and SME. The results show that the SME in both the CoAl and the CoNi alloys results from the stress-induced HCP martensite. The role of the thermal HCP martensite in both of them is the strengthening of the matrix. The much higher yield strength in the solution-treated CoAl alloy due to solution strengthening of Al is responsible for its better SME compared with the CoNi alloy.

EFFECT OF MICROSTRUCTURE ON THE HARDENING AND SOFTENING BEHAVIORS OF POLYCRYSTALLINE SHAPE MEMORY ALLOYS PART Ⅰ:MICROMECHANICS CONSTITUTIVE MODELING

The effects of microstructure and its evolution on the macroscopic superelastic stress-strain response of polycrystalline Shape Memory Alloy(SMA)are studied by a microstructure-based constitutive model developed in this paper.The model is established on the following basis:(1)the transformation conditions of the unconstrained single crystal SMA microdomain(to be distinguished from the bulk single crystal),which serve as the local criterion for the derivation of overall transfor- mation yield conditions of the polycrystal;(2)the micro-to macro-transition scheme by which the connection between the polycrystal aggregates and the single crystal microdomain is established and the macroscopic transformation conditions of the polycrystal SMA are derived;(3)the quantitative incorporation of three microstruc- ture factors(i.e.,nucleation,growth and orientation distribution of martensite)into the modeling.These microstructural factors are intrinsic of specific polycrystal SMA systems and the role of each factor in the macroscopic constitutive response is quan- titatively modeled.It is demonstrated that the interplay of these factors will result in different macroscopic transformation kinematics and kinetics which are responsible for the observed macroscopic stress-strain hardening or softening response,the latter will lead to the localization and propagation of transformation bands in TiNi SMA.

Influences of 2.5wt%Mn addition on the microstructure and mechanical properties of Cu-Al-Ni shape memory alloys

The influences of 2.5wt%Mn addition on the microstructure and mechanical properties of the Cu-11.9wt%Al-3.8wt%Ni shape memory alloy（SMA） were studied by means of scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,and differential scanning calorimeter（DSC）.The experimental results show that Mn addition influences considerably the austenite-martensite transformation temperatures and the kind of martensite in the Cu-Al-Ni alloy.The martensitic transformation changes from a mixedβ1→β＇1＋γ＇1 transformation to a singleβ1→β＇1 martensite transformation together with a decrease in transformation temperatures.In addition,the observations reveal that the grain size of the Cu-Al-Ni alloy can be controlled with the addition of 2.5wt%Mn and thus its mechanical properties can be enhanced.The Cu-Al-Ni-Mn alloy exhibits better mechanical properties with the high ultimate compression strength and ductility of 952 MPa and 15%,respectively.These improvements are attributed to a decrease in grain size.However,the hardness decreases from Hv 230 to Hv 140 with the Mn addition.

Transformation behavior and shape memory effect of Ti_(50-x)Ni_(48)Fe_2Nb_x alloys by aging treatment

The influence of aging treatment on transformation behavior and shape memory of the Ti 50_x Ni_(48) Fe_2 Nb_x(x=0,0.6,0.8,1.0,and 1.2) alloys was investigated using differential scanning calorimeter(DSC),mechanical drawing machine,and microhardness tester in this paper.It is indicated that the aging treatment has a significant effect on the phase transformation temperatures(M_s,M_f,M_p,A_s,A_f,and A_p) and microhardness of the samples.The phase transformation temperatures are found to decrease initially with the increasing aging temperature from 300 to 500 ℃ and increase with further increase of the aging temperature.The aging treatment at intermediate temperature between 400 and 500 ℃ results in an improved shape memory effect.In addition,the highest microhardness value is also obtained.

Microstructure and corrosion behavior of NiTi shape memory alloys sintered in the SPS process

NiTi shape memory alloys(SMAs) was developed using the spark-plasma sintering(SPS) process with different average particle size(45 μm and 10 μm) under various temperature. The influence of particle size and temperature on the density, microstructure, and corrosion behavior of the NiTi in simulated body fluid was examined. The porosity decreased with increasing sintering temperature and decreasing particle size, which resulted in an increase in density of the alloy. Increasing the sintering temperature led to the formation of Ni-and Ti-rich intermetallic such as Ni3Ti and NiTi2. The formation of these secondary phases influenced the corrosion behavior of NiTi by changing its chemical composition. The planar structure of NiTi was transformed into a dendritic structure at 900℃, which resulted in the formation of uniform oxide and phosphate layers on the entire surface. A high corrosion potential and low corrosion current density were achieved with NiTi prepared with 10 μm particles at 900℃, which exhibited superior corrosion resistance.

Review on non-conventional machining of shape memory alloys

Shape memory alloys （SMAs） are the developing advanced materials due to their versatile specific properties such as pseudoelasticity, shape memory effect （SME）, biocompatibility, high specific strength, high corrosion resistance, high wear resistance and high anti-fatigue property. Therefore, the SMAs are used in many applications such as aerospace, medical and automobile. However, the conventional machining of SMAs causes serious tool wear, time consuming and less dimensional deformity due to severe strain hardening and pseudoelasticity. These materials can be machined using non-conventional methods such as laser machining, water jet machining （WJM） and electrochemical machining （ECM）, but these processes are limited to complexity and mechanical properties of the component. Electrical discharge machining （EDM） and wire EDM （WEDM） show high capability to machine SMAs of complex shapes with precise dimensions. The aim of this work is to present the consolidated references on the machining of SMAs using EDM and WEDM and subsequently identify the research gaps. In support to these research gaps, this work has also evolved the future research directions.

Microstructural,mechanical and shape memory characterizations of Ti-Mo-Sn alloys

As a β stabilizing element in Ti-based alloys,the effect of Mo on phase constitution,microstructure,mechanical and shape memory properties was investigated.Different compositions of Ti-xMo-3Sn alloys(where x=2,4,6,at.%) were prepared by arc melting.A binary composition of Ti-6 Mo alloy was also prepared for comparison.Ti-xMo-3Sn alloys show low hardness and high ductility with 90% reduction in thickness while Ti-6 Mo alloy shows high hardness,brittle behavior,and poor ductility.Field emission scanning electron microscopy(FESEM) reveals round morphology of athermal ω(ωath) precipitates.The presence of ωath phase is also confirmed by X-ray diffraction(XRD)in both as-cast and solution-treated and quenched conditions.The optical microscopy(OM) and FESEM show that the amount of martensite forming during quenching decreases with an increase in Mo content,which is also due to β→ω transformation.The hardness trends reinforce the presence of ωath too.The shape memory effect(SME) of 9% is the highest for Ti-6 Mo-3Sn alloy.The SME is trivial due to ωath phase formation;however,the increase in SME is observed with an increase in Mo content,which is due to the reverse transformation from ωath and the stress-induced martensitic transformation.In addition,a new and very simple method was designed and used for shape memory effect measurement.

Force-displacement characteristics of simply supported beam laminated with shape memory alloys

As a preliminary step in the nonlinear design of shape memory alloy（SMA） composite structures,the force-displacement characteristics of the SMA layer are studied.The bilinear hysteretic model is adopted to describe the constitutive relationship of SMA material.Under the assumption that there is no point of SMA layer finishing martensitic phase transformation during the loading and unloading process,the generalized restoring force generated by SMA layer is deduced for the case that the simply supported beam vibrates in its first mode.The generalized force is expressed as piecewise-nonlinear hysteretic function of the beam transverse displacement.Furthermore the energy dissipated by SMA layer during one period is obtained by integration,then its dependencies are discussed on the vibration amplitude and the SMA＇s strain（Ms-Strain） value at the beginning of martensitic phase transformation.It is shown that SMA＇s energy dissipating capacity is proportional to the stiffness difference of bilinear model and nonlinearly dependent on Ms-Strain.The increasing rate of the dissipating capacity gradually reduces with the amplitude increasing.The condition corresponding to the maximum dissipating capacity is deduced for given value of the vibration amplitude.The obtained results are helpful for designing beams laminated with shape memory alloys.

Martensitic transformation in Cu-doped NiMnGa magnetic shape memory alloys

This paper studies the martensitic transformation in the Cu-doped NiMnGa alloys. The orthorhombic martensite transforms to L21 cubic austenite by Cu substituting for Ni in the Nis0-xCuxMn31Ga19 （x=2 10） alloys, the martensitic transformation temperature decreases significantly with the rate of 40 K per Cu atom addition. The variation of the Fermi sphere radius （kF） is applied to evaluate the change of the martensitic transformation temperature. The increase of kF leads to the increase of the martensitic transformation temperature.

EFFECT OF MICROSTRUCTURE ON THE HARDENING AND SOFTENING BEHAVIORS OF POLYCRYSTALLINE SHAPE MEMORY ALLOYS PART Ⅱ:NUMERICAL SIMULATION UNDER AXISYMMETRICAL LOADING

Based on the microstructure-based constitutive model established in Part Ⅰ,a detailed numerical investigation on the role of each microstructure pa- rameter in the kinematical and kinetic evolution of polycrystalline SMA under ax- isymmetrical tension loading is performed.Some macroscopic constitutive features of stress-induced martensite transformation are discussed.

Phase Transformation and Thermal Stability of Aged Ti-Ni-Hf High Temperature Shape Memory Alloys

The use of Ni-rich TiNiHf alloys as high temperature shape memory alloys （SMAs） through aging has been presented. For Ni-rich Ti80-xNixHf20 alloys, their phase transformation temperatures are averagely increased more than 100 K by aging at 823 K for 2 h. Especially for the alloys with Ni-content of 50.4 at. pct and 50.6 at. pct, their martensitic transformation start temperatures （Ms） are more than 473 K after aging. TEM observation confirmed that some fine particles precipitate from the matrix during aging. The aged Ni-rich TiNiHf SMAs show the better thermal stability of phase transformation temperatures than the solutiontreated TiNiHf alloys. The fine particles precipitated during aging should be responsible for the increase of phase transformation temperatures and its high stability.