Nickel-titanium shape memory alloys made by selective laser melting:a review on process optimisation

Selective laser melting (SLM) is a mainstream powder-bed fusion additive manufacturing (AM) process that creates a three-dimensional (3D) object using a high power laser to fuse fine particles of various metallic powders such as copper, tool steel, cobalt chrome, titanium, tungsten, aluminium and stainless steel. Over the past decade, SLM has received significant attention due to its capability in producing dense parts with superior mechanical properties. As a premier shape memory alloy, the nickel-titanium (NiTi) shape memory alloy is attractive for a variety of biomedical applications due to its superior mechanical properties, superelasticity, corrosion resistance and biocompatibility. This paper presents a comprehensive review of the recent progress in NiTi alloys produced by the SLM process, with a particular focus on the relationship between processing parameters, resultant microstructures and properties. Current research gaps, challenges and suggestions for future research are also addressed.The full text can be downloaded at https://link.springer.com/article/10.1007/s40436-021-00376-9     

Influence of Ti Powder Characteristics on Combustion Synthesis of Porous NiTi Alloy

Porous NiTi shape memory alloy (SMA) is a novel biomedical material used for human hard tissue implant .The influence of elemental titanium powder characteristics such as powder morphology, particle size and specific surface area( SSA) on the minimal ignition temperature ,combustion temperature and final product of porous Ni-Ti SMA fabricated by combustion synthesis method was investigated in this paper by scanning electron microscopy (SEM) and laser diffraction.The preliminary data indicated that the titanium powder characteristics had a strong effect on combustion synthesis of porous NiTi SMA.     

Niobium Wires as Space Holder and Sintering Aid for Porous NiTi

When NiTi powder compacts containing Nb wires are heated above 1 170 °C, each Nb wire reacts with adjacent NiTi powders to form a eutectic liquid which wicks into the space between the remaining NiTi powders. This creates a macropore at the location of the Nb wire while eliminating the microporosity between NiTi powders which is filled with a NiTi/Nb eutectic phase after solidification. This novel method produces – in a single step and without applied pressure – a dense NiTi matrix with elongated pores suitable for shape memory or superelastic applications such as bone implants, dampeners and actuators.     

Fabrication and characterization of NiTi shape memory alloy synthesized by Ni electroless plating of titanium powder

In this work NiTi shape memory alloy was fabricated from mixed elemental powders, Ni plated titanium powder and Ni heated/plated titanium powder by Ar-sintering. Electroless plating process was utilized to fabricate Ni plated titanium powder. For this purpose titanium powder was plated in an electroless Ni bath for 225?min and hydrazine hydrate was used as a reductant to deposit pure nickel on the titanium particles. Ni plated titanium powder was heat treated under an argon atmosphere at 1000?°C to prepare Ni heated/plated titanium powder. Finally, the three sample powders were pressed by CIP followed by sintering at 980?°C for 8?h to manufacture NiTi shape memory alloy. The prepared powders, as well as sintered samples, were characterized by scanning electronic microscopy (SEM), energy dispersive spectrometer analysis (EDS), X-ray fluorescence (XRF), X-ray diffraction (XRD) and differential scanning calorimetric (DSC). The results indicated the presence of NiTi phase and also non-transformable phases (NiTi₂ and Ni₃Ti) in the heated/plated Ti powder and sintered samples. NiTi compound was dominated phase in the heated/plated sintered sample. All three sintered samples, as well as heated/plated powder, showed one-step phase transformation (B2???B19′).     

化学修饰对NiTi形状记忆合金氧化膜的影响

用X光电子能谱（XPS）研究了NiTi形状记忆合金经酸、碱处理后表面氧化膜成分和结构的变化。结果表明，未经处理的NiTi合金表面最外层氧化膜主要由TiO2、TiO和少量的Ni组成，酸、碱处理后，最外层氧化膜由TiO2、Ni2O3组成，但经碱处理后，氧化膜的厚度大大增加。     

Manufacturing and processing of NiTi implants: A review

NiTi is categorized as a shape memory alloy that found interesting applications in vast areas of engineering from aerospace to biomedical; the latter applications are due to its biocompatibility in addition to its unique properties. The unique properties such as shape memory and pseudoelasticity make NiTi an excellent candidate in many functional designs. However, the manufacturing and processing complications of this alloy pose impediments to widespread applications. This paper discusses challenges and opportunities in making NiTi parts for biomedical applications such as implants. To this end, common manufacturing processes for NiTi from casting and powder metallurgy to machining are discussed. Also, new opportunities in additive manufacturing processes such as laser and electron beam techniques towards making 3D components from NiTi are described. Finally, the challenges in heat treatment and shape-setting of NiTi parts in order to attain desired shape memory properties are reviewed.     

Shape Memory Effect,Thermal Expansion and Damping Property of Friction Stir Processed NiTip/Al Composite

NiTi particles reinforced aluminum(NiTip/Al) composite was prepared via friction stir processing,eliminating interfacial reaction and/or elemental diffusion.The NiTip in the composite maintained the intrinsic characteristic of a reversible thermoelastic phase transformation even after heat-treatment.The shape memory characteristic of the NiTip decreased the coefficient of thermal expansion of the Al matrix,and an apparent two-way shape memory effect was observed in the composite.The composite owned a good combination of adjustable damping and thermal physical properties.     

Shape memory effect in porous volume NiTi articles fabricated by selective laser sintering

The shape memory effect in porous nickel titanium (NiTi) articles obtained by means of layered synthesis using selective laser sintering (SLS) technology was studied by measuring the temperature dependence of the electric resistivity of the material. For the porous NiTi samples synthesized from Ni and Ti powders, the interval of probable appearance of the shape memory effect falls within the temperature interval from −50 to 0°C. In a porous material synthesized by laser sintering from a commercial NiTi powder of the PV N55T45 grade, this effect falls in the interval from +25 to +50°C. Prospects for the use of porous NiTi articles as medicinal implants are discussed.     

Analysis of the mechanical and shape memory behaviour of nitrogen ion-implanted NiTi alloy

Experimental results of an accumulation and return strain behaviour of the modified surface of NiTi alloy, as well as mechanical and shape memory behaviour, are shown in this paper.Surface of equiatomic NiTi shape memory alloy (in martensitic form) has been modified by high-dose ion-implantation technique using nitrogen ion beam. The low-energy (65 keV) and following high doses have been used: 1×10¹⁷, 5×10¹⁷ and 1×10¹⁸ J/cm². Correlation between subsurface layers elemental composition of NiTi alloy, microstructure and shape memory properties is shown.     

PM‐Composites with Nickel‐Titanium Shape Memory Alloys

Starting from NiTi‐powders, composites of nickel‐titanium shape memory alloys (NiTi‐SMA) and different stainless steels as well as of different NiTi‐SMAs were produced by using the process of hot isostatic pressing (HIP). Metallographic investigations focussed on the interface between NiTi‐SMA and stainless steel with special emphasis placed on the characterization of the typical structure of the diffusion zones in both components.     

Metal injection molding of shape memory alloys using prealloyed NiTi powders

Metal injection molding (MIM) was applied for the production of shape memory parts using prealloyed NiTi powders with different Ni contents as starting materials. The MIM process allows the production of near-net-shape components without the occurrence of rapid tool wear as found in the case of conventional machining operations. With optimized manufacturing conditions, including feedstock preparation, injection parameters and sintering conditions, densities of more than 98% of the theoretical value could be achieved. Determination of the phase transformation behavior, as a basic requirement for the shape memory effect, was done by differential scanning calorimetry (DSC). In a first approach, tensile tests in the austenitic state showed pseudoelastic behavior. An elongation at failure of 3.8% was found. For martensite, up to 5% was obtained. Reasons for the lower strain compared to melted NiTi alloys are discussed. For martensitic samples the one-way shape memory effect (1WE) was demonstrated.     

Processing and property assessment of NiTi and NiTiCu shape memory actuator springs

Among the multifarious engineering applications of NiTi shape memory alloys (SMAs), their use in actuator applications stands out. In actuator applications, where the one‐way effect (1WE) of NiTi SMAs is exploited, SM components are often applied as helical coil springs. Ingots are generally used as starting materials for the production of springs. But before SM actuator springs can be manufactured, the processing of appropriate wires from NiTi ingots poses a challenge because cold and hot working of NiTi SMAs strongly affect microstructure, and it is well known that the functional properties of NiTi SMAs are strongly dependent on their microstructure. The objective of the present paper is therefore to produce binary Ni₅₀Ti₅₀ and ternary Ni₄₀Ti₅₀Cu₁₀ SMA actuator springs, starting from ingots produced by vacuum induction melting. From these ingots springs are produced using swaging, rolling, wire drawing and a shape‐constraining procedure in combination with appropriate heat treatments. The evolution of microstructure during processing is characterized and the mechanical properties of the wires prior to spring‐making are documented. The mechanical and functional characteristics of the wires are investigated in the stress‐strain‐temperature space. Finally, functional fatigue testing of actuator springs is briefly described and preliminary results for NiTi and NiTiCu actuator springs are reported.     

NiTi合金形状记忆效应的微观机制研究进展

NiTi合金具有优异的形状记忆功能和良好的生物体兼容性,近年来对它的应用研究受到工程界和医学界的重视,同时对NiTi合金形状记忆效应的微观机制的研究也在逐步深入.介绍了NiTi合金的主要特性及影响其形状记忆功能的主要因素,总结了NiTi合金的形状记忆效应和超弹性的微观机制研究现状,并指出了需对该合金进一步研究的一些问题.     

Pore structures of high-porosity NiTi alloys made from elemental powders with NaCl temporary space-holders

The unusual pseudo-elasticity and shape memory effect make NiTi alloys promising energy absorption materials. In the present study, powders of Ti, Ni and NaCl particles were mixed and cold-pressed into green ingots and green ingots were then desalted and sintered in vacuum to form high-porosity NiTi alloy specimens with porosity up to 90%. Microstructure observation shows that two kinds of pores with sizes of 200-400 μm and 10-50 μm respectively are well-distributed in these high-porosity NiTi alloys. Characteristics of pores were studied and formation mechanism was discussed.     

Combustion synthesis/quasi-isostatic pressing of TiC–NiTi cermets: processing and mechanical response

TiC–NiTi composites were produced by a technique combining self-propagating high-temperature synthesis (SHS) of elemental powders of Ni, Ti, and C with densification by quasi-isostatic pressing (QIP). In order to create a one-step synthesis/densification process, the Ti + Ni + C reactant material was surrounded in a bed of graphite and alumina particulate before initiation of the combustion reaction. The sample was ignited within the particulate and subjected to a uniaxial load immediately after passage of the combustion wave. The constitutive response, composition and resulting structures of the composites with varying volume fractions of NiTi are characterized. Powder mixtures prepared anticipating the formation of stoichiometric TiC result in the formation of composites with a eutectic matrix of Ni₃Ti and NiTi. This titanium impoverishment of the matrix is consistent with the formation of nonstoichiometric TiC _x during the combustion reaction. The Ni₃Ti phase can be suppressed by anticipating the formation of TiC_0.7 and adjusting the chemical content of the reactant mixture to include additional titanium. These cermets combine the high hardness of the ceramic phase with the possible shape memory and superelastic effects of NiTi.     

Phase composition and wear behavior of NiTi alloys

This study deals with the wear behavior of two NiTi shape memory alloys, one of them being martensitic, the other one austenitic at room temperature. Wear tests have been conducted with a disk-on-block geometry. The block was made of the NiTi alloy, whereas counterface disk materials were AISI M2 high-speed steel and a WC–Co hardmetal. From the evolution of the friction coefficient and temperature during the tests and from the characterization of the wear debris and traces, it has been possible to identify the main wear mechanisms. In the wear tests involving the M2 steel disk, both NiTi alloys display a transition, as a function of the applied load, from a mainly oxidation regime to a more complex situation, in which oxidation wear is accompanied by delamination of metallic alloy fragments. Higher wear rates of the shape memory alloys have been observed for the NiTi/WC–Co coupling. In this case, a transition from a mainly delamination wear to a regime featuring a mixture of delamination and oxidation wear has been observed.     

三元Ni-Ti基形状记忆合金的研究现状

针对二元NiTi形状记忆合金在应用中所显示出的局限性,三元NiTi基形状记忆合金通过第三组元的加入,改善了二元NiTi形状记忆合金的某些性能,弥补了其在应用中的不足,降低了成本,进一步扩大了NiTi基形状记忆合金的应用范围,从而一直受到研究者的广泛关注.综述了三元NiTi基形状记忆合金的研究现状,总结了存在的不足:首先,对于合金体系还需要大量的量化研究,确定出不同应用条件下合金的有效成分范围是其实用化的基础;其次,合金制备过程熔炼介质对合金产生的影响等重视不够;同时,应用性能研究还有待加强,性能的长效性与稳定性是关键,这方面的研究还缺乏充分而有效的数据.     

热机械循环方法对训练NiTi合金双程形状记忆效应的影响

采用4种典型的热机械循环方法训练获取具有双程形状记忆效应的镍钛合金丝,从双程形状回复量、高温相形状、低温相形状和相变温度的变化等方面系统研究了训练方法对双程形状记忆效应训练效果的影响.结果表明,在不同训练方法中镍钛合金丝被加载应变时所处的物质相态的差异是造成不同训练效果的主要原因,其中在马氏体相变过程中因加栽引入的位错最有利于双程形状记忆效应的形成.     

Mechanical activation of pre-alloyed NiTi<Subscript>2</Subscript> and elemental Ni for the synthesis of NiTi alloys

This work reports on an efficient powder metallurgy method for the synthesis of NiTi alloys, involving mechanical activation of pre-alloyed NiTi₂ and elemental Ni powders (NiTi₂–Ni) followed by a press-and-sinter step. The idea is to take advantage of the brittle nature of NiTi₂ to promote a better efficiency of the mechanical activation process. The conventional mechanical activation route using elemental Ti and Ni powders (Ti–Ni) was also used for comparative purposes. Starting with (NiTi₂–Ni) powder mixtures resulted in the formation of a predominant amorphous structure after mechanical activation at 300 rpm for 2 h. A sintered specimen consisting mainly of NiTi phase was obtained after vacuum sintering at 1050 °C for 0.5 h. The produced NiTi phase exhibited the martensitic transformation behavior. Using elemental Ti powders instead of pre-alloyed NiTi₂ powders, the structural homogenization of the synthesized NiTi alloys was delayed. Performing the mechanical activation at 300 rpm for the (Ti–Ni) powder mixtures gave rise to the formation of composite particles consisting in dense areas of alternate fine layers of Ni and Ti. However, no significant structural modification was observed even after 16 h of mechanical activation. Only after vacuum sintering at 1050 °C for 6 h, the NiTi phase was observed to be the predominant phase. The higher reactivity of the mechanically activated (NiTi₂–Ni) powder particles can explain the different sintering behavior of those powders compared with the mechanically activated (Ti–Ni) powders. It is demonstrated that this innovative approach allows an effective time reduction in the mechanical activation and of the vacuum sintering step.     

Detecting NiTi two-way shape memory effect based on microstructural and macromechanical parameters

ABSTRACT

The two-way shape memory effect in NiTi shape memory alloys is identified according to the evolution of the apparent modulus of the martensite during mechanical cycling. The microstrain and texture index of the NiTi samples are evaluated with synchrotron data to relate the evolution to the changes in the NiTi microstructure caused by mechanical cycling. The results show that a progressive decrease in the apparent modulus of the martensite during load, together with an increase in the apparent modulus of the reoriented martensite, are a sign that the NiTi sample is developing the two-way memory effect by mechanical cycling. When the two moduli show the same value, the two-way shape memory effect is fully developed in the NiTi alloy.

This paper is part of a thematic issue on Titanium.