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     

Selective laser melting of high aspect ratio 3D nickel–titanium structures two way trained for MEMS applications

Selective laser melting has been used to build high aspect ratio, three-dimensional NiTi micro-electro-mechanical components. Cantilever beams manufactured in this way have been two-way trained and actuated by ohmic heating demonstrating the suitability of the process for applications in micro-electromechanical technologies. The influence of laser dwell time and raster pitch on the density of NiTi shape memory alloy parts and the resolvable feature sizes achievable are discussed. The shape memory effect properties of solid parts produced by selective laser melting are also reported in contrast to those properties exhibited by NiTi alloys resulting from other processes.     

NiTi合金生物医用材料表面改性的研究进展

NiTi合金由于其形状记忆效应、超弹性和低模量等优良性能在生物医学领域得到广泛应用。然而,在生理环境中镍离子释放会诱发毒性和炎性反应,因此需要对其进行表面改性。从表面氧化、表面涂层和表面接枝大分子等方面综述了近年来国内外NiTi合金表面改性的研究进展,评述了各种表面改性技术的优势和缺陷,指明了NiTi合金表面改性的未来发展趋势。     

Formation of microporous NiTi by transient liquid phase sintering of elemental powders

Porous metallic structures are attractive for biomedical implant applications as their open porosity simultaneously improves the degree of fixation and decreases the mismatch in stiffness between bone and implant, improving bonding and reducing stress-shielding effects respectively. NiTi alloys exhibit both the shape memory effect and pseudoelasticity, and are of particular interest, though they pose substantial problems in their processing. This is because the shape memory and pseudoelastic behaviours are exceptionally sensitive to the presence of oxygen, and other minor changes in alloy chemistry. Thus in processing careful control of composition and contamination is vital. In this communication, we investigate these issues in a novel technique for producing porous NiTi parts via transient liquid phase sintering following metal injection moulding (MIM) of elemental Ni and Ti powders, and report a new mechanism for pore formation in the powder processing of metallic materials from elemental powders.     

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.     

Biocompatibility and corrosion behavior of the shape memory NiTi alloy in the physiological environments simulated with body fluids for medical applications

Due to unique properties of NiTi shape memory alloys such as high corrosion resistance, biocompatibility, super elasticity and shape memory behavior, NiTi shape memory alloys are suitable materials for medical applications. Although TiO₂ passive layer in these alloys can prevent releasing of nickel to the environment, high nickel content and stability of passive layer in these alloys are very debatable subjects. In this study a NiTi shape memory alloy with nominal composition of 50.7 atom% Ni was investigated by corrosion tests. Electrochemical tests were performed in two physiological environments of Ringer solution and NaCl 0.9% solution. Results indicate that the breakdown potential of the NiTi alloy in NaCl 0.9% solution is higher than that in Ringer solution. The results of Scanning Electron Microscope (SEM) reveal that low pitting corrosion occurred in Ringer solution compared with NaCl solution at potentiostatic tests. The pH value of the solutions increases after the electrochemical tests. The existence of hydride products in the X-ray diffraction analysis confirms the decrease of the concentration of hydrogen ion in solutions. Topographical evaluations show that corrosion products are nearly same in all samples. The biocompatibility tests were performed by reaction of mouse fibroblast cells (L929). The growth and development of cells for different times were measured by numbering the cells or statistics investigations. The figures of cells for different times showed natural growth of cells. The different of the cell numbers between the test specimen and control specimen was negligible; therefore it may be concluded that the NiTi shape memory alloy is not toxic in the physiological environments simulated with body fluids.     

Surface hardening of NiTi shape memory alloy induced by the nanostructured layer after surface mechanical attrition treatment

To conduct grain refinement induced by plastic deformation, NiTi shape memory alloy is processed by surface mechanical attrition treatment. The process leads to surface nanocrystallization and consequently surface hardening. The cross sectional microhardness of the treated NiTi is measured and compared to those of annealed NiTi specimens with residual stress relaxation and recrystallization. Our results show that surface nanocrystallization induced by surface mechanical attrition treatment is an effective method to enhance the surface hardness and anti-wear properties of NiTi shape memory alloy for the biomedical application.     

Selective laser melting of NiTi alloy with superior tensile property and shape memory effect

It is a challenge to develop complex-shaped NiTi shape memory alloy parts by traditional processing methods, due to the poor machinability of NiTi alloy. It is reported that selective laser melting (SLM) of additive manufacturing could overcome this problem. However, the reported SLM-produced NiTi exhibits poor tensile ductility due to the inner defects and adverse unidirectional columnar grains from SLM process. In this work, the defect-less SLM-NiTi with nondirective columnar grains was fabricated by optimizing the intraformational laser scanning length and interformational laser scanning direction. The obtained lath-shaped SLM-NiTi sample exhibits tensile strain of 15.6%, more than twice of the reported maximum result (˜7%). Besides, the SLM-NiTi part with complex geometry displays a shape memory recovery of 99% under compressive deformation of 50%.     

NiTi形状记忆合金在生物医用领域的研究进展

NiTi形状记忆合金由于具有良好的力学相容性、耐蚀性和生物相容性而在生物医用材料领域得到广泛应用。本文总结了医用NiTi形状记忆合金的研究现状,评述了NiTi形状记忆合金的耐蚀性和生物相容性特点,并详细讨论了NiTi形状记忆合金的表面改性问题,对NiTi形状记忆合金的医用前景进行了展望。     

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.     

镍钛合金在医疗器械领域应用和表面改性研究进展

镍钛合金基于特有的超弹性、形状记忆效应,广泛应用于医疗器械领域。其中超弹性表现为大变形下的弹性应变,应用于血管和腔道介入器械、口腔正畸丝、根管器械等;形状记忆效应可实现低温下易变形、体温下自回复,应用于热激活正畸丝、骨科、矫形外科、缝线等。此外,可通过多样化的表面改性技术,提升镍钛合金的生物相容性、腐蚀抗性、摩擦磨损性能,优化产品性能,拓展其在医疗器械制品中的应用范围。     

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。     

NiTi合金生物医用材料表面改性的研究进展

NiTi形状记忆合金作为重要的生物医用材料已经获得了广泛的应用,但Ni离子在人体环境中的释放引起了人们的忧虑.系统介绍了近年来表面改性提高NiTi合金生物相容性的主要方法、技术特点和优势.在众多的研究方法中,热氧化和自组装方法因具有工艺简单、成本低等优点而最具工业应用前景.有关NiTi合金表面涂层与细胞和血液的相互作用机理的研究亟待加强,微观方面应重视基因水平的评价,宏观方面应加强活体植入的研究.研究机构应与产业界密切配合,进一步推动相关涂层的产业化进程.     

Heat Treatment of Ni-Ti Alloy for Improvement of Shape Memory Effect

Nickel-Titanium alloys with stoichiometric single phase and non-stoichiometric dual phase structures of NiTi and NiTi+Ni3Ti are produced through high speed induction melting and combustion synthesis of pure Ti/Ni elements. Both alloys are homogenized at 1273 K for two hours, rolled into thin strips of 0.3 mm thickness, solution treated at 1273 K for two hours under vacuum and finally quenched in water. Effect of ageing on austenite/martensite and intermediate phase transformation temperatures are investigated. Results show that transformation temperatures and reversible shape memory properties comparable with those required for bioengineering applications such as manufacturing of artificial hand prostheses can be obtained through careful control of the chemical composition and the heating processes.     

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.     

Relevant aspects in the clinical applications of NiTi shape memory alloys

NiTi shape memory alloys showing pseudoelastic behaviour have great potential in dental and orthopaedic applications where constant correcting loads may be required. In most of the clinical applications the device may have been heat treated and during its life in service it will be cyclically deformed. It is therefore important to investigate the effect of cyclic straining and heat treatments upon the transformation stresses and temperatures of the material. The aim of this work is to study the thermal and mechanical ageing of a pseudoelastic NiTi shape memory alloy, as well as the environmental in vitro degradation of the alloy due to the effect of artificial saliva.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials, Oporto, Portugal, 10–13 September.     

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.     

Dissolution effect and cytotoxicity of diamond-like carbon coatings on orthodontic archwires

Nickel–titanium (NiTi) has been used for implants in orthodontics due to the unique properties such as shape memory effect and superelasticity. However, NiTi alloys are eroded in the oral cavity because they are immersed by saliva with enzymolysis. Their reactions lead corrosion and nickel release into the body. The higher concentrations of Ni release may generate harmful reactions. Ni release causes allergenic, toxic and carcinogenic reactions. It is well known that diamond-like carbon (DLC) films have excellent properties, such as extreme hardness, low friction coefficients, high wear resistance. In addition, DLC film has many other superior properties as a protective coating for biomedical applications such as biocompatibility and chemical inertness. Therefore, DLC film has received enormous attention as a biocompatible coating. In this study, DLC film coated NiTi orthodontic archwires to protect Ni release into the oral cavity. Each wire was immersed in physiological saline at the temperature 37 °C for 6 months. The release concentration of Ni ions was detected using microwave induced plasma mass spectrometry (MIP-MS) with the resolution of ppb level. The toxic effect of Ni release was studied the cell growth using squamous carcinoma cells. These cells were seeded in 24 well culture plates and materials were immersed in each well directly. The concentration of Ni ions in the solutions had been reduced one-sixth by DLC films when compared with non-coated wire. This study indicated that DLC films have the protective effect of the diffusion and the non-cytotoxicity in corrosive environment.     

Inhomogeneous structure of near-surface layers in the ion-implanted NiTi alloy

This paper reports the application of nitrogen ion implantation for modification of a shape memory alloy. It is known that the problem of creating a protective surface coating for the shape memory alloy is the most acute for potential applications of this material. Thus, the problem of increasing surface protective properties and, at the same time, simultaneous preservation of functional properties of shape memory materials is a subject of research and development [Pelletier H, Muller D, Mille P, Grob J. Surf Coat Technol 2002;158:309.]. The surface characterization of nitrogen implanted (fluence 10¹⁸ cm^?2 and energy 50 keV) equiatomic commercial NiTi alloy samples was performed with the assistance of high resolution transmission electron microscopy (HTEM) techniques and modifications of phase composition before and after irradiation are studied at room and martensitic transformation temperatures by X-ray diffraction methods. Differential scanning calorimetry (DSC, TA Instruments) was used to characterize the transformation sequence and transformation temperatures for the initial and surface-modified materials. Experimental results of an inhomogeneous structure of near-surface layers in the ion-implanted NiTi alloy are discussed in this paper.