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.

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.

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.

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.

Effects of Ta Addition on NiTi Shape Memory Alloys

The effect of Ta addition on the martensitic transformation characteristics and the X-ray visibility on NiTi shape memory alloy have been studied in (Ni51Ti49)1-xTax system. It was found that the transformation temperatures of the Ni51Ti49 binary alloy increased drastically by an addition of 0～4 at. pet Ta, but only slightly when the concentration exceeded 4 at. pct; the addition of Ta greatly decreases the sensitivity of the martensitic transformations to the variation in the Ni-Ti ratio. The addition of Ta to the NiTi binary alloy can improve its X-ray visibility.

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.

Martensitic Transformation in Fe-Mn-Si Based Shape Memory Alloys

The critical driving force for martensitic transformation fcc ( gamma ) yields hcp ( epsilon ) in ternary Fe-Mn-Si alloys increases with the content of Mn and decreases with that of Si. Thermodynamical prediction of M//s in ternary Fe-Mn-Si alloys was established. The fcc ( gamma ) yields hcp ( epsilon ) martensitic transformation in Fe-Mn-Si is a semi-thermoelastic and the nucleation process does not strongly depend on soft mode. Nucleation occurs directly through an overlapping of stacking fault rather than pole mechanism, and it is suggested that stacking fault energy (SFE) is the main factor controlling nucleation. Based on the phenomenological theory of martensite crystallography, a shuffle on (0001)//h//c//p plane is required when d//1//1//1 does not equal d//0//0//0//2. The derived principal strain in Bain distortion is smaller, i, e., more reasonable than the values given by Christian. Alloying elements strengthening the austenite, lowering SFE of gamma phase and reducing T//N** gamma temperature may be beneficial to shape memory effect of Fe-Mn-Si based alloys. Accordingly, Fe-Mn-Si-RE and Fe-Mn-Si-Cr-N (or Fe-Mn-Si-Ni-Cr-N) are worthy to be recommended as shape memory materials with improved shape memory effect. (Edited author abstract) 48 Refs.

Martensite Aging Effect and Thermal Cyclic Characteristics in Ti-Pd and Ti-Pd-Ni High Temperature Shape Memory Alloys

The effect of thermal cycling and aging in martensitic state in Ti-Pd-Ni alloys were investigated by DSC and TEM observations. It is shown that the thermal cycling causes the decreases in M, and Af temperatures in Ti50Pd50-xNix (x=10, 20, 30) alloys, but no obvious thermal cycling effect was observed in Ti50Pd50Pd40Ni10 alloys and the aging effect shows a curious feature, i.e., the Af temperature does not saturate even after relatively long time aging, which is considered to be due to the occurrence of recovery recrystallization during aging.

Surface Coating of NiTi Shape Memory Alloys with Calcium Phosphates by Dip-coating or Plasma-spraying-biological Characterization Examined by in vitro Testing Methods

The influence of different surface coatings of NiTi shape memory allays was examined using in vitro testing methods. Plates of superelastic nickel-titanium shape memory allay （ NiTi ） were coated with calcium phosphates （ hydroxyapatite ） by high-temperature plasma-spraying or by dip-coating. The biocompatibility was tested in vitro by cultivation of isolated human granulocytes and whole blood cells. As substrates, pure NiTi, plasma-spray-coated NiTi and dip-coated NiTi were used. Isolated granulocytes showed an increased adhesion to both calcium phosphate-coated NiTi samples. Compared to non-coated NiTi or dip-coated NiTi, the number of dead granulocytes adherent to plasma-sprayed surfaces was significantly increased （ p 〈 0.01 ）. Whether the d/f- ferences in apoptosis of granulocytes on dip-coated vs plasma-sprayed coatings observed are due to differences in material surface morphologies has to be analyzed in further studies. Because of the cellular interactions with the coating layers, h is likely that the results obtained are not caused by the underlying NiTi but due to the coating itself.

Formation Mechanism of Curved Martensite Structures in Cu-based Shape Memory Alloys

The curved martensite structures have been observed in CuZnAI-based shape memory alloys by both transmission electron microscope and optical microscope. It was found that the curved martensite structures observed in as-solution treated, as-aged and as-trained alloys usually occurred around dislocation tangles or precipitate, at the plate boundary or grain boundary, and when the growing plates collided with each other or alternate mutually.

Martensitic stabilization and defects induced by deformation in TiNi shape memory alloys

Martensitic stabilization caused by deformation in a TiNi shape memory alloy was studied.Special attention was paid to the deformed microstructures to identify the cause of martensitic stabilization.Martensitic stabilization was demonstrated by differential scanning calorimetry for the tensioned TiNi shape memory alloy.Transmission electron microscopy revealed that antiphase boundaries were formed because of the fourfold dissociation of [110]B19＇ super lattice dislocations and were preserved after reverse transformation due to the lattice correspondence.Martensitic stabilization was attributed to dislocations induced by deformation,which reduced the ordering degree of the microstructure,spoiled the reverse path from martensite to parent phase compared with thermoelastic transformation,and imposed resistance on phase transformation through the stress field.

High temperature strain glass in Ti–Au and Ti–Pt based shape memory alloys

Strain glass is a frozen short-range strain ordered state found in shape memory alloys recently, which exhibits novel properties around the ideal glass transition temperature T_(0). However, the T_(0) of current strain glass systems is still very low, limiting their potential applications and experimental studies. In this paper, we reported two new strain glass systems with relatively high T_(0). In Ti_(50)Au_(50-x)Cr_(x) alloys, the strain glass appears at x = 25, and exhibits a T_(0) of 251 K, while in Ti_(50)Pt_(50-y)Fey alloys, the strain glass takes place at y = 30, and shows a T_(0) of 272 K. Both of them are comparable with the highest T_(0) value reported so far. Moreover, the phase diagrams of main strain glass systems in Ti-based alloys were summarized. It is found that the influence of the martensitic transformation temperature of the host alloy on the T_(0) of the strain glass is limited. This work may help to design new strain glass systems with higher T_(0) above ambient temperature.

EFFECTS OF RARE EARTH MIXTURE ON MECHANICAL PROPERTIES OF CuZnAl SHAPE MEMORY ALLOYS

With thehelpofquantitative metallograph ,tensiletest,electron probeandscan electron mi croscope,theinfluencesof mixture rareearth ( RE) on the grain size, dynamics of grain growth and mechanicalpropertiesof CuZnAlshape memoryalloys wereinvestigated . Theex perimentalresultsshowsthat REcanrefinegrainsgreatly,improvethe mechanicalpropertiesremarkably andchangethetensilefracturefrom brittletypebordered grainstoplastictypeinthecondition of maintainingshape memory properties. Moreover microstructuresrevealthatREwhich accumulates on the grain boundariescan restrain grains’growing. In addition, the mechanismsofrefininggrainsizeandimproving mechanicalpropertiesarealsodiscussed.

Three dimensional large deformation analysis of phase transformation in shape memory alloys

Shape memory alloys（SMAs）have been explored as smart materials and used as dampers,actuator elements,and smart sensors.An important character of SMAs is its ability to recover all of its large deformations in mechanical loading-unloading cycles without showing permanent deformation.This paper presents a stress-induced phenomenological constitutive equation for SMAs,which can be used to describe the superelastic hysteresis loops and phase transformation between Martensite and Austenite.The Martensite fraction of SMAs is assumed to be dependent on deviatoric stress tensor.Therefore,phase transformation of SMAs is volume preserving during the phase transformation.The model is implemented in large deformation finite element code and cast in the updated Lagrangian scheme.In order to use the Cauchy stress and the linear strain in constitutive laws,a frame indifferent stress objective rate has to be used.In this paper,the Jaumann stress rate is used.Results of the numerical experiments conducted in this study show that the superelastic hysteresis loops arising with the phase transformation can be effectively captured.

A CONSTITUTIVE RELATION FOR PSEUDO-ELASTIC BEHAVIOUR IN SHAPE MEMORY ALLOYS

A constitutive relation to describe pseudo-elastic deformation in shape memory alloys is pres- ented in this paper. It is capable of describing deformation behaviour of polycrystalline materials under triaxial stress state as well as of monocrystalline materials under one-dimensional condition. Total strain rate is sup- posed to be composed of elastic strain rate and transformation strain rate. Deformation behaviour of Cu-Zn-Sn alloy and Ti-Ni alloy is simulated by use of the proposed constitutive relation. It is shown that simulated results are in a good agreement with experimental data.

Pressure effects on magnetic properties and martensitic transformation of Ni–Mn–Sn magnetic shape memory alloys

The mechanism for the effects of pressure on the magnetic properties and the martensitic transformation of Ni-Mn- Sn shape memory alloys is revealed by first-principles calculations. It is found that the total energy difference between paramagnetic and ferromagnetic austenite states plays an important role in the magnetic transition of Ni-Mn-Sn under pressure. The pressure increases the relative stability of the martensite with respect to the anstenite, leading to an increase of the martensitic transformation temperature. Moreover, the effects of pressure on the magnetic properties and the martensitic transformation are discussed based on the electronic structure.

Effect of Co on magnetic property and phase stability of Ni-Mn-Ga ferromagnetic shape memory alloys:A first-principles study

The effect of Co content on magnetic property and phase stability of Ni50-xMn25Ga25Cox ferromagnetic shape memory alloys has been investigated using first-principles calculations. The total energy difference between paramagnetic and ferromagnetic state of austenite plays an important role in the magnetic transition. The high Curie temperature can be attributed to the stronger Co-Mn exchange interaction as compared to the Ni-Mn one. The phase stability of Niso-xMn25Ga25Cox austenite increases with increasing Co content, which is discussed based on the electronic structure.

The effect of Fe on the martensitic transformation of TaRu high-temperature shape memory alloys:A first-principles study

The effect of Fe on the martensitic transformation of TaRu high-temperature shape memory alloys has been investigated using first-principles calculations.The site preference of Fe in TaRu alloys has been clarified for the first time,and the results show that Fe is predicted to occupy Ru sites.The addition of Fe increases the stability of the Ta 50 Ru 50 x Fe x β phase,leading to a significant decrease in the β to β ＇ martensitic transformation temperature.In addition,the mechanism of the Fe alloying effect is explained on the basis of the electronic structure.

ON THE STRAIN JUMP IN SHAPE MEMORY ALLOYS—A CRYSTALLOGRAPHIC-BASED MECHANICS ANALYSIS

The strain jump across the Austenite-Martensite (A-M) interface in single crystal Cu-14wt%Al-4.12wt%Ni Shape Memory Alloys (SMAs) under uniaxial tension was studied in this paper. A crystallographic-based mechanics analysis on the formation and microstructure of the interface was performed. By using the high sensitive Moiré interference technique, the full-field deformation patterns during the transformation process were successfully recorded. The orientation of the habit plane (A-M interface) and the magnitude of the shape strain were determined precisely from the Moiré fringe patterns. The theoretical predictions on the habit plane normal and the shape strain were compared with the measured results and good agreements were obtained.

ESTIMATION OF LOCAL HYSTERETIC PROPERTIES FOR SHAPE MEMORY ALLOYS

The applicability of shape memory alloys (SMAs) in structural dynamics,particularly as hysteretic damping elements, is limited by the difficulties in modelling theirdeformation characteristics. At typical engineering design levels of loading SMAs exhibitpseudo-elastic properties. A combined experimental and simulation approach suitable for thecharacterisation of novel smart devices based on the pseudo-elastic effect is described.