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。     

Corrosion behavior of a laser-welded NiTi shape memory alloy

Corrosion behaviors of the laser-welded Ni–49.4 at.% Ti shape memory alloy and base metal in 0.9% NaCl solution were investigated by means of electrochemical techniques (the open circuit potential measurement, linear and potentiodynamic polarizations). The results showed that corrosion resistance of the laser-welded NiTi alloy is better than that of the base metal. Compared to the base metal, the laser-welded NiTi alloy exhibits higher open circuit potential, higher polarization resistance, a wider passive region and higher breakdown potential. The improvement of corrosion resistance of the laser-welded NiTi alloy is ascribed to a smoother, defect free surface and an absence of carbides.     

On the electropolishing of NiTi braided stents – challenges and solutions

Nickel Titanium (NiTi) alloys possess special mechanical properties and good biocompatibility hence used as base material for the production of vascular stents. Normally, vascular stents are machined from NiTi tubes, using laser cutting processes. Braiding is a promising alternative for the machining of certain NiTi stents. However, a surface finish treatment, such as electropolishing of the braided stents, is still required in order to achieve a medical‐grade surface finish. The thermally‐grown oxide resulting from the shape‐setting heat treatment, following the braiding must be removed. Moreover, electropolishing is required to achieve optimum corrosion resistance. Therefore, the aim of this study is to find suitable parameters for the effective electropolishing of NiTi textile stents. Electropolishing of a device with such a complex geometry is challenging, hence a custom‐designed electrolytic cell was constructed and used in this study. We examined the stent surfaces before and after electropolishing, using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). Potentiodynamic tests were performed in NaCl 0.9% solution for as‐received and electropolished samples. The results from the present study indicate an improvement in surface quality of the braided stents after electropolishing. Potentiodynamic tests revealed that electropolishing improves the corrosion resistance of the NiTi stents.     

Effects of microstructural mechanisms on the localized oxidation behavior of NiTi shape memory alloys in simulated body fluid

Localized oxidation and corrosion behavior of a nickel–titanium (NiTi) shape memory alloy (SMA) was investigated via static immersion experiments in a simulated body fluid solution. Detailed electron microscopy examinations on the sample surfaces revealed preferential formation of local oxide particles around dislocation networks, which constitute high-energy zones. Moreover, various intermediate phases were detected in addition to the parent NiTi phase around dislocation networks. These are also areas with enhanced diffusion, which promotes Ni release. These findings emphasize the significant role of fine microstructural features, such as dislocation networks, on the oxidation and Ni release, and thus, the biocompatibility of the NiTi SMAs.     

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。     

3.5%NaCl腐蚀环境下2种航空铝合金材料疲劳性能试验研究

腐蚀环境下的疲劳性能是航空金属结构疲劳寿命设计的重要前提,为此,试验测定了2种航空铝合金材料（2E12-T3、7050-T7451）的光滑试样和缺口试样在干燥大气和3.5%NaCl腐蚀环境下的疲劳性能,在试验数据的基础上进行性能对比,并对试样断口进行扫描电镜（SEM）分析,研究了3.5%NaCl腐蚀环境与载荷联合作用对腐蚀疲劳性能的影响机理,研究结果表明:3.5%NaCl腐蚀环境对2种铝合金材料的疲劳性能均产生不利影响,且腐蚀与疲劳载荷的交互作用随着应力水平的降低而增强,疲劳性能下降更明显;与光滑试样相比,腐蚀环境对铝合金2E12-T3缺口试样疲劳性能的影响更大,但对铝合金7050-T7451缺口试样疲劳性能的影响却变小;在腐蚀环境下,裂纹尖端易发生电化学反应产生腐蚀产物和[H]离子,腐蚀产物的存在会阻碍裂纹闭合,同时,[H]离子导致裂纹尖端的氢脆效应,加快裂纹扩展,使疲劳性能降低。     

Influence of the microstructure on electrochemical corrosion and nickel release in NiTi orthodontic archwires

The aim of this work was to determine the influence of the present phases and the chemical composition on the corrosion behavior and the nickel ion release of the NiTi orthodontic archwires. Eight Ni–Ti archwires from six commercial brands, in the as-received condition, were studied. The chemical composition, roughness, microstructure and the proportion of the phases as well as the corrosion behavior were analyzed for each archwire. The nickel ion release was characterized in artificial saliva immersion settings ranging up to 4 weeks. The results show that the presence of the martensitic phase improves corrosion resistance and significantly decreases Ni release into exterior medium in comparison with the austenitic specimens. In spite of the partial loss of superelasticity produced in the martensitic phase, it could be of great interest for biomedical applications, as it could minimize sensitization and allergies and improve biocompatibility and corrosion resistance of NiTi shape memory alloys.     

Corrosion behavior of a low modulus β-Ti-45%Nb alloy for use in medical implants

The corrosion and electrochemical behavior of a low stiffness β -Ti-45wt.%Nb (Ti45Nb) was studied in solutions that resemble body environment, as compared to Ti6Al4V and Ti-55wt.%Ni (Ti55Ni, Nitinol) alloys currently used in surgical implants. In Ringers' solution, Ti45Nb alloy exhibited an excellent corrosion resistance, comparable to that of Ti6Al4V and much better than that of Nitinol. In acidic environments, β -Ti45Nb remained passive under conditions where active dissolution was observed for both Ti6Al4V and Nitinol alloys. The results warrant further corrosion and biocompatibility studies of β -Ti45Nb alloy to establish its suitability as implant material.     

Nitinol surface roughness modulates in vitro cell response: a comparison between fibroblasts and osteoblasts

The purpose of the present in vitro study was to examine the biocompatibility of a nickel–titanium (NiTi) shape memory alloy. Human gingival fibroblastic and rat embryo osteoblastic cells were cultured on NiTi discs. The discs were prepared with two surface roughnesses. Cell response to these surfaces was compared for the two types of cells. The comparison was based on an analysis of the cell morphology, adhesion and proliferation rates. Fibronectin labeling by immunofluorescence staining was also performed. For osteoblastic cells, alkaline phosphatase assay was conducted as a function of NiTi surface roughness and for different durations.     

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。     

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.     

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     

Deposition of Bioactive Layer on NiTi Alloy by Chemical Treatment

A simple chemical method was developed for inducing bioactivity on NiTi alloys(50 at.pct by Ni/Ti).A layer of calcium phosphate was deposited on the surface to improve biocompatibility of thealloy.NiTi alloys were first etched in HNO3 aqueous solution,and then treated with boiling diluted NaOH solution.A rough surface was created and a thin TiO2 layer was formed on the surface.Pre-calcification was then introduced by immersing the treated NiTi alloys in supersaturated Na2HPO4 solution and supersaturated Ca(OH)2 solution in turn before calcification in simulated body fluid (SBF).A dense and uniform bonelike calcium phosphate(Ca-P) bioactive layer was formed on the surfaces of the specimen,which would improve their biocompatibility.Morphology and element analysis on NiTi surfaces during the treatments were investigated in detail by means of environment scanning electron microscopy(ESEM),energy dispersion X-ray spectroscopy(EDXS),and X-ray diffraction (XPD).     

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.     

Study of the in vitro corrosion behavior and biocompatibility of Zr-2.5Nb and Zr-1.5Nb-1Ta (at%) crystalline alloys

The in vitro corrosion behavior and biocompatibility of two Zr alloys, Zr-2.5Nb, employed for the manufacture of CANDU reactor pressure tubes, and Zr-1.5Nb-1Ta (at%), for use as implant materials have been assessed and compared with those of Grade 2 Ti, which is known to be a highly compatible metallic biomaterial. The in vitro corrosion resistance was investigated by open circuit potential and electrochemical impedance spectroscopy (EIS) measurements, as a function of exposure time to an artificial physiological environment (Ringer’s solution). Open circuit potential values indicated that both the Zr alloys and Grade 2 Ti undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Zr-1.5Nb-1Ta alloy and that this oxide has better corrosion protection characteristics than the ones formed on Grade 2 Ti or on the Zr-2.5Nb alloy. EIS study showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The fit obtained suggests a single passive film presents on the metals surface, improving their resistance with exposure time, presenting the highest values to the Zr-1.5Nb-1Ta alloy. For the biocompatibility analysis human osteosarcoma cell line (Saos-2) and human primary bone marrow stromal cells (BMSC) were used. Biocompatibility tests showed that Saos-2 cells grow rapidly, independently of the surface, due to reduced dependency from matrix deposition and microenvironment recognition. BMSC instead display a reduced proliferation, possibly caused by a reduced crosstalk with the metal surface microenvironment. However, once the substrate has been colonized, BMSC seem to respond properly to osteoinduction stimuli, thus supporting a substantial equivalence in the biocompatibility among the Zr alloys and Grade 2 titanium. In summary, high in vitro corrosion resistance together with satisfactory biocompatibility make the Zr-2.5Nb and Zr-1.5Nb-1Ta crystalline alloys promising biomaterials for surgical implants.     

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.     

NiTi shape memory alloys coated with calcium phosphate by plasma‐spraying. Chemical and biological properties

Plates of superelastic nickel‐titanium shape memory alloy (NiTi) were coated with calcium phosphate (hydroxyapatite) by high‐temperature plasma‐spraying. The porous layer of about 100 μm thickness showed a good adhesion to the metallic substrate that withstood bending of the plate but detached upon cutting the plate. The biocompatibility was tested by cultivation of blood cells (whole blood and isolated granulocytes [a subpopulation of blood leukocytes]). As substrates, pure NiTi, plasma‐spray‐coated NiTi and calcium phosphate‐coated NiTi prepared by a dip‐coating process were used. The adhesion of whole blood cells to all materials was not significantly different. In contrast, isolated granulocytes showed an increased adhesion to both calcium phosphate‐coated NiTi samples. However, compared to non‐coated NiTi or dip‐coated NiTi, the number of dead granulocytes adherent to plasma‐sprayed surfaces was significantly increased for isolated granulocytes (p<0.01).     

Improving the biocompatibility of NiTi alloy by chemical treatments: An in vitro evaluation in 3T3 human fibroblast cell

The nearly equi-atomic nickel titanium alloy was coated with calcium phosphates by socking the chemically treated alloy in simulated body fluid in order to prepare bioactive NiTi implants. The biocompatibility of the calcium phosphates coated NiTi alloy was investigated by in vitro 3T3 human embryonic fibroblast cell culture tests. The cells attachment and morphologies were studied using phase contrast light microscope and environmental scanning electron microscope. The mechanically polished and the calcium phosphates coated NiTi samples were well tolerated by the cells, whereas, the controlled pure Ni samples exhibited strong toxicity to the cells. Furthermore, the calcium phosphates coated NiTi samples showed good osteoconductivity.     

In vitro corrosion behaviour of Ti–Nb–Sn shape memory alloys in Ringer’s physiological solution

The nearly equiatomic Ni–Ti alloy (Nitinol) has been widely employed in the medical and dental fields owing to its shape memory or superelastic properties. The main concern about the use of this alloy derives form the fact that it contains a large amount of nickel (55% by mass), which is suspected responsible for allergic, toxic and carcinogenic reactions. In this work, the in vitro corrosion behavior of two Ti–Nb–Sn shape memory alloys, Ti–16Nb–5Sn and Ti–18Nb–4Sn (mass%) has been investigated and compared with that of Nitinol. The in vitro corrosion resistance was assessed in naturally aerated Ringer’s physiological solution at 37°C by corrosion potential and electrochemical impedance spectroscopy (EIS) measurements as a function of exposure time, and potentiodynamic polarization curves. Corrosion potential values indicated that both Ni–Ti and Ti–Nb–Sn alloys undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Ti–18Nb–5Sn alloy. Significantly low anodic current density values were obtained from the polarization curves, indicating a typical passive behaviour for all investigated alloys, but Nitinol exhibited breakdown of passivity at potentials above approximately 450 mV(SCE), suggesting lower corrosion protection characteristics of its oxide film compared to the Ti–Nb–Sn alloys. EIS studies showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The obtained EIS spectra were analyzed using an equivalent electrical circuit representing a duplex structure oxide film, composed by an outer and porous layer (low resistance), and an inner barrier layer (high resistance) mainly responsible for the alloys corrosion resistance. The resistance of passive film present on the metals’ surface increases with exposure time displaying the highest values to Ti–18Nb–4Sn alloy. All these electrochemical results suggest that Ti–Nb–Sn alloys are promising materials for biomedical applications.     

Bio-corrosion characterization of Mg–Zn–X (X = Ca, Mn, Si) alloys for biomedical applications

The successful applications of magnesium-based alloys as biodegradable orthopedic implants are mainly inhibited due to their high degradation rates in physiological environment. This study examines the bio-corrosion behaviour of Mg–2Zn–0.2X (X = Ca, Mn, Si) alloys in Ringer’s physiological solution that simulates bodily fluids, and compares it with that of AZ91 magnesium alloy. Potentiodynamic polarization and electrochemical impedance spectroscopy results showed a better corrosion behaviour of AZ91 alloy with respect to Mg–2Zn–0.2Ca and Mg–2Zn–0.2Si alloys. On the contrary, enhanced corrosion resistance was observed for Mg–2Zn–0.2Mn alloy compared to the AZ91 one: Mg–2Zn–0.2Mn alloy exhibited a four-fold increase in the polarization resistance than AZ91 alloy after 168 h exposure to the Ringer’s physiological solution. The improved corrosion behaviour of the Mg–2Zn–0.2Mn alloy with respect to the AZ91 one can be ascribed to enhanced protective properties of the Mg(OH)₂ surface layer. The present study suggests the Mg–2Zn–0.2Mn alloy as a promising candidate for its applications in degradable orthopedic implants, and is worthwhile to further investigate the in vivo corrosion behaviour as well as assessed the mechanical properties of this alloy.