NiTi合金中马氏体相的低频力学谱研究

我们用最近研制成功的LMA型低频力学谱测试系统对NiTi合金马氏体相进行了在很大频率范围内（0．003～1Hz）的低频等温力学谱和温度谱的测量．我们研究的形状记忆合金NiTi（Ni50．2at％）试样长34mm，直径1mm细丝．经一定热处理，分别在333K．343K和353K做了内耗随频率的变化的测量。实验表明：频率越小，内耗越大，也就是内耗随频率减少而增大。同时我们采用阶梯升温的方法在八个温度下每个温度测量三种频率（1Hz，0．1Hz，0．01Hz）的内耗，结果清楚地表明：不同频率下，内耗峰都出现在372K（99℃）。而且频率越低，峰高越高。这是具有相变峰的特点：相变峰的峰温不随测量频率不同而变化，相变峰高度随频率减少而增大。我们还测量了在1Hz与0．5Hz频率下内耗随温度的变化。本文用马氏体相的位错理论初步讨论了上述实验结果。     

Assessing the biocompatibility of NiTi shape memory alloys used for medical applications

The present paper reviews aspects related to the biocompatibility of NiTi shape memory alloys used for medical applications. These smart metallic materials, which are characterised by outstanding mechanical properties, have been gaining increasing importance over the last two decades in many minimal invasive surgery and diagnostic applications, as well as for other uses, such as in orthodontic appliances. Due to the presence of high amounts of Ni, the cytotoxicity of such alloys is under scrutiny. In this review paper we analyse work published on the biocompatibility of NiTi alloys, considering aspects related to: (1) corrosion properties and the different methods used to test them, as well as specimen surface states; (2) biocompatibility tests in vitro and in vivo; (3) the release of Ni ions. It is shown that NiTi shape memory alloys are generally characterised by good corrosion properties, in most cases superior to those of conventional stainless steel or Co–Cr–Mo-based biomedical materials. The majority of biocompatibility studies suggest that these alloys have low cytotoxicity (both in vitro and in vivo) as well as low genotoxicity. The release of Ni ions depends on the surface state and the surface chemistry. Smooth surfaces with well-controlled structures and chemistries of the outermost protective TiO₂ layer lead to negligible release of Ni ions, with concentrations below the normal human daily intake.     

Surface characteristics and electrochemical behaviour of sputter-deposited NiTi thin film

Thin nanocrystalline amorphous NiTi film was deposited on Si substrate using DC magnetron sputtering. The as-deposited NiTi thin film was crystallized by heat treatment at 500 °C for 1 h. The crystal structure, surface morphology, microstructure and surface chemistry of the deposited films were studied using X-ray diffraction, atomic force microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy (XPS), respectively. Corrosion behaviour was assessed in Ringer’s solution at 37 °C by open circuit potential (OCP), potentiodynamic polarization and electrochemical impedance spectroscopy as a function of exposure time. OCP values indicate that the tendency for the formation of a spontaneous oxide film is greater for the NiTi thin films than the bulk NiTi. Long time exposure to Ringer’s solution was found to have a great effect on the corrosion behaviour of the samples. Significantly low corrosion current density was obtained for the annealed NiTi film from the potentiodynamic polarization curves indicating a typical passive behaviour, but as-deposited film and bulk NiTi alloy exhibited breakdown of passivity at potentials approximately +1.4 V (vs. SCE). XPS showed that the oxide film formed on the annealed NiTi thin film mainly composed of Ti oxides, and no evidence of Ni was found up to 8.2 nm beneath the top surface, suggesting the excellent corrosion resistance of this sample in Ringer’s solution.     

Laser welding of thin foil nickel-titanium shape memory alloy

In this study, two L27 Taguchi experiments were carried out to study the effect of fibre laser welding parameters and their interactions upon the weld bead aspect ratio of nickel-titanium thin foil. The optimum parameters to produce full penetrated weld with the largest aspect ratio and desirable microstructure were successfully obtained by the Taguchi experimental design. The corrosion property of the optimized NiTi weld in Hank’s solution at 37.5 °C was studied and compared with the as-received NiTi. To improve the corrosion properties of the weld, the effect of post-weld-heat-treatments ranging from 573 to 1173 K was investigated. The corrosion properties, surface morphology, microstructure and Ti/Ni ratio of the heat-treated NiTi weld were analysed. It was found that a post-weld heat treatment at 573 K for 1 h provided the best pitting corrosion resistance at the weld zone.     

利用光杠杆法测量金属丝的弹性滞后环

利用大学物理实验中的光杠杆法测定金属丝弹性模量的原理和设备,对具有超弹性的NiTi丝的弹性滞后环进行了测定结果表明,此种方法可以很好地测定NiTi丝的弹性滞后环,而且操作简单使用方便,是一种非常有效的测定金属细丝弹性滞后环的方法.     

热处理对NiTi形状记忆合金冲蚀磨损性能的影响

采用自制浆罐式砂水冲蚀磨损试验装置研究了4种经不同条件热处理的NiTi合金与1Cr18Ni9Ti不锈钢的冲蚀磨损性能;采用XL-30型扫描电子显微镜观察试样的冲蚀磨损表面形貌;采用MH-6型显微硬度计测量NiTi合金硬度;采用自制拉伸装置测量NiTi合金的力学性能.结果表明:5种试样的冲蚀磨损量随着冲蚀时间、冲蚀速度、砂水比及砂粒度的增加而增大,4种NiTi合金的耐冲蚀性能相近,均明显优于1Cr18Ni9Ti不锈钢,其中试样NiTi-3和NiTi-1表现出较好的耐冲蚀性能;硬度并非NiTi合金冲蚀磨损性能的决定因素,超弹性和超塑性是NiTi合金具有较好耐冲蚀性的主要原因,热处理使得NiTi合金的超弹性变形量减小,但增加了NiTi合金的塑性变形量;合金丝磨损表面不同部位的磨损机理不同,中部为典型的变形磨损,侧面为微切削磨损,5种试样均表现为典型的韧性材料冲蚀磨损特征.     

医用多孔NiTi合金表面溶胶-凝胶法制备TiO2涂层

采用溶胶-凝胶法结合浸渍提拉工艺在多孔NiTi合金表面制备出了结构均一的锐钛矿型TiO2涂层,并在溶胶中添加聚乙二醇(PEG)作为造孔剂,进而在多孔NiTi合金表面制备出内层致密、外层多孔的TiO2复合涂层。SEM分析结果表明,TiO2涂层均匀地覆盖了多孔NiTi合金基体的外表面以及孔的内表面。Hanks溶液中的阳极极化曲线结果表明,与未处理的多孔NiTi合金相比,具有致密TiO2涂层的多孔NiTi合金其耐腐蚀性能有了显著提高。而多孔TiO2复合涂层进一步增大了多孔NiTi合金的实际表面积,提高了材料表面的生物活性。     

An Electrochemical Robotic System for Routine Cathodic Adsorptive Stripping Analysis of Ni2+ Ion Release from Corroding NiTi Shape Memory Alloys

Cathodic adsorptive stripping voltammetry (AdSV) as highly sensitive and selective method for quantifying trace amounts of dissolved Ni²⁺‐ions has been integrated into an electrochemical robotic device using the wells of microtiter plates as low‐volume electrochemical cells. A three‐electrode assembly integrating a Bismuth film‐modified glassy carbon electrode as working electrode and a glass capillary for delivering Ni²⁺ standard solution in conjunction with an adapted software allowed multiple AdSV measuring cycles to be performed one after the other in the individual compartments of a 24‐well microtiter plate. Of advantage for the automation was the possibility of an in‐well electrochemical removal of used and a replating of fresh Bi films in between distinct measuring cycles. With optimized parameters for the accumulation of the complex between Ni²⁺‐ions and dimethylglyoxime onto the surface of the Bi film electrode and the subsequent stripping procedure, automated adsorptive stripping voltammetry in the established system offered a linear dynamic range of up to 170 nM, a sensitivity of 12 nA/nM Ni²⁺ and a limit of of detection of 2.1 nM (N=16) for the detection of trace levels of Ni²⁺‐ions. Automated AdSV certainly is of convenience for studying larger number of samples due to the high‐throughput capability of the robotic apparatus. As example, the automatic quantification of Ni²⁺‐ion release from electropolished surfaces of NiTi shape memory alloys during corrosion in NaCl solutions is described.     

Nb掺杂影响NiTi金属间化合物电子结构的第一性原理计算

采用基于密度泛函理论(DFT)的第一性原理平面波超软赝势方法,计算了Nb元素掺杂对B2构型NiTi金属间化合物电子结构的影响.点缺陷生成能的计算结果表明,Nb原子掺杂后,NiTi中产生Ni原子和Ti原子空位和反位点缺陷所需要的能量均明显升高;态密度计算结果表明,Nb原子掺杂后与临近原子发生了明显的s-s, p-p和d-d电子相互作用,增加了与临近原子之间的电荷密度,有利于Nb与合金原子的成键.这些由Nb掺杂所导致的NiTi电子结构和键合特征的变化均有利于促进Nb与合金原子的相互作用,在一定程 关键词： NiTi金属间化合物 点缺陷 电子结构 第一性原理计算     

Marker experiments to determine diffusing species and diffusion path in medical Nitinol alloys

The out-diffusion of toxic Ni ions from NiTi (Nitinol), often used for biomedical applications, can be strongly reduced using oxygen plasma immersion ion implantation (PIII). Non-radioactive isotope markers, ⁶⁰Ni and ⁴⁶Ti, were implanted at 180 keV into NiTi prior to the oxygen implantation with fluences between 0.4 × 10¹⁶ and 4 × 10¹⁶ at./cm². Implanting oxygen ions by PIII in the temperature range of 400-550 °C leads to a surface oxide layer consisting of pure TiO₂. The results prove that Ni cations are the mobile species, while Ti is immobile during the oxygen insertion.