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...     

NiTi形状记忆合金表面改性的研究进展

近等原子比的NiTi合金以其优异的特性在临床医学得到广泛应用,但是由于Ni离子溶出引致的潜在生物毒性以及无生物活性,抑制了NiTi合金在生物医用领域的进一步发展。为了改善上述缺陷,对NiTi合金进行表面处理成为当前国内外NiTi合金研究的热点。从不同的改性工艺出发,全面阐述了近年来国内外对致密态和多孔态NiTi合金进行表面改性的研究进展,对各种方法可能出现的问题进行了分析,指出现有的各种表面改性方法不能有效实现对多孔NiTi合金内部孔隙进行改性,并针对这一症结提出了采用原位氮化法对多孔NiTi合金进行改性的可行性。     

医用NiTi形状记忆合金表面氧化改性研究进展

氧化是NiTi形状记忆合金表面改性的重要手段,常用的氧化工艺包括热氧化、微弧氧化、阳极氧化和化学氧化。虽然四种工艺都依靠合金自身的Ti元素在合金表面原位生成以晶态或非晶态TiO2为主的氧化膜,但四种氧化工艺的原理及所制备的膜层形貌、结构等均不相同。本文评述了四种表面改性工艺的优势和缺陷,并对NiTi合金表面改性的发展方向进行了展望。     

NiTi 合金表面激光原位反应合成TiN增强金属基复合材料涂层

采用连续高功率固体Nd-YA G激光辐照, 使预置于NiTi 合金表面的Ti 粉在N₂ 环境中形成TiN 增强Ti 基复合材料涂层。选择适当的激光辐照工艺参数, 获得致密的TiN 增强金属基复合材料激光改性层。SEM 观察及EDAX 成分分析结果表明, TiN/ Ti 金属基复合材料表面改性层与基体NiTi 合金存在良好的冶金结合, 界面处成分均匀过渡, 表面Ni 含量极低。显微硬度测试及磨损实验表明, TiN/ Ti 金属基复合材料改性层显著提高了NiTi 合金的表面硬度和耐磨性, 激光表面改性层可有效地改善NiTi 合金作为生物医学材料使用的表面成分和性能。      

NiTi合金表面液相阴极等离子体沉积氧化铝陶瓷涂层的研究

在NiTi合金表面通过液相阴极等离子体技术制备了氧化铝(Al2O3)陶瓷涂层。采用X射线衍射和扫描电镜对涂层的相组成以及表面形貌进行了表征和分析,证实在材料表面形成了由α-Al2O3和γ-Al2O3组成的涂层,发现涂层具有粗糙多孔结构。在模拟体液中对NiTi合金的Ni离子释放情况进行了检测,发现液相阴极等离子体改性后显著降低了Ni离子的释放。为NiTi合金植入体的表面改性提供了一条新途径。     

医用NiTi合金表面改性的研究进展

近等原子比NiTi合金具有独特的力学性能,如形状记忆效应、超弹性和高阻尼效应,已成为一种新型的整形外科植入材料.但是,镍元素在生理条件下可能溶出,诱发毒性和炎性反应,限制了其在临床的广泛应用.分类介绍了几种可行的表面改性方法,均能有效地抑制镍离子的溶出,改善NiTi合金的抗腐蚀性和生物相容性,包括表面惰性涂层化、表面氧化、表面活性化和表面接枝大分子等.     

表面氧化及离子注氮对NiTi形状记忆合金耐腐蚀性能的影响

采用电化学测试的方法，研究了表面氧化以及表面氧化-离子注氮两种表面改性方式对NiTi形状记忆合金在人体生理模拟液(Hank′s溶液)中腐蚀行为的影响。腐蚀电位和极化曲线的测量结果表明表面氧化-离子注氮的方法使NiTi合金材料的腐蚀电位正移。雏钝电流密度下降，钝化电位区间扩大，合金表面耐蚀性明显提高。尤其是NiTi合金在进行氮离子注入后，测得击穿电位显著上升．增强了表面膜的抗局部腐蚀能力。因而表面氧化-离子注氮的改性方法可使材料的耐蚀性达到最佳。通过XPS的分析发现，离子注氮后合金表面形成氮化钛相以及富含羟基的化学效应，使NiTi基体的电化学性能得到提高。     

离子束合成TiO2薄膜对医用NiTi合金表面的改性

采用离子束增强沉积法制备TiO2薄膜,对医用NiTi合金进行表面改性处理。系统研究了薄膜的表面组成、结构、形貌及耐蚀性、亲水性等与血液相容性相关的表面性质。NiTi合金表面沉积TiO2薄膜后,抗模拟体液的腐蚀性提高,凝血时间延长。为进一步提高TiO2薄膜的抗凝血性,对TiO2薄膜的进一步表面改性－表面结合肝素分子进行了初步尝试,结果表明,薄膜表面组成发生变化,表面亲水性进一步提高。     

不同温度下纯Ni/NiTi合金的摩擦特性研究

NiTi合金具有形状记忆效应及超弹性特性,使得它与其他一般材料的摩擦特性有很大不同。为从微观角度揭示其摩擦特性,利用分子动力学研究了不同温度下纯Ni和NiTi合金的压/划痕过程,并进一步通过对比分析不同温度下纯Ni和NiTi合金在压/划痕过程中原子结构、表面形貌、摩擦力和摩擦系数的变化,研究了温度对NiTi合金摩擦系数的影响。结果表明,温度对NiTi合金摩擦性能的影响显著,在300～500 K范围内,温度越低,摩擦力与摩擦系数越小,这是由于在刻划过程中NiTi合金发生马氏体相变,NiTi合金表面向下凹陷,减少了NiTi表面与压头的接触,降低了对压头的阻碍,使摩擦力与摩擦系数大幅降低;当温度升高时,马氏体相变减少,NiTi合金的表面凹陷减少,使压头与NiTi合金的接触面积增大,阻碍增大,从而使得摩擦力和摩擦系数变大。而没有相变机制的金属Ni在刻划过程中,主要产生塑性形变,温度对其摩擦性能无显著影响。可见,温度对NiTi形状记忆合金的摩擦性能具备一定调控能力,可以通过控制温度达到减少磨损的目的,这可为延长NiTi合金元件的使用寿命提供理论基础和指导。     

激光表面改性对NiTi形状记忆合金腐蚀行为的影响

采用连续波Nd：YAG固体激光,在NiTi形状记忆合金表面制备出表面致密、无7L洞和裂纹的氮化层,测试了这种激光改性层在37℃模拟人体体液Hank’s溶液中的电化学阳极极化曲线和交流阻抗谱,研究了改性层的腐蚀行为．结果表明,NiTi合金氮化层的腐蚀电位和击穿电位正移,反应转移电阻明显提高,而腐蚀电流及界面电容下降．这说明激光气体氮化有效地改善了NiTi形状记忆合金在模拟人体体液中的电化学抗腐蚀性能．     

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.     

多孔NiTi合金的化学氧化处理表面改性研究

在H2O2+HCl溶液中对多孔NiTi合金进行了化学氧化处理表面改性。利用EPMA、SEM、原子吸收光谱对合金表面氧化膜的组成、形貌及化学氧化处理前后的Ni离子释出进行了研究。结果表明,经过H2O2+HCl溶液化学氧化表面处理后合金表面Ni含量显著降低,在生理盐水中的Ni释放速率明显下降;H2O2+HCl溶液浓度和氧化时间均对合金表面氧化膜的生长有较大影响。     

Fabrication and biocompatibility of polyethyleneimine/heparin self-assembly coating on NiTi alloy

NiTi alloy has been used widely as biomaterials. But because of toxic effects possibly caused by excess Ni ions released during the corrosion process in the physiological environment, it is still a controversial material. Fabricating medicine-loaded coating, which is expected to decrease the release of Ni ions and improve the biocompatibility of the materials, is a potential way to solve the problem. In this paper, NiTi alloy is coated by polyethyleneimine/heparin films via layer-by-layer (LBL) self-assembly method. UV-Vis, FT-IR, atomic force microscopy (AFM) and contact angle measurements are used to characterize the microstructure of coatings and select the best fabrication conditions. Potentiodynamic polarization researches in sodium chloride and dynamic clotting time experiment are utilized to study its corrosion resistance capability and biocompatibility of coatings, respectively. The results indicate that PEI/heparin multilayer coating can improve the biocompatibility of NiTi alloy surface.     

NiTi superelastic orthodontic archwires with polyamide coating

Twenty orthodontic archwires with 55.2 % Ni and 44.8 % Ti (% weight) were subjected to a dipping treatment to coat the NiTi surface by a polyamide polymer. It has been selected a Polyamide 11 due to its remarkable long lasting performance. The transformation temperatures as well as the transformation stresses of the NiTi alloy were determined in order to know whether the coating process can alter its properties. The adhesive wear tests have been demonstrated that the wear rates as well as the dynamic friction coefficients μ of polymer coated wires are much lower than metallic wires. The corrosion studies have shown that the use of this polymer, as coating, seals the NiTi surface to prevent corrosion and the release of nickel ions. The average decrease of Ni ions release due to this coating is around 85 %.     

Surface modification of NiTi alloy and human platelet activation under static and flow conditions

The effect of surface nickel species on NiTi alloy thrombogeneity was investigated by assessment of platelet activation and whether oxidative modification of the alloy would affect platelet response. Tests were conducted under static conditions and arterial levels of shear stress. Heat treatment of the alloy at 600 °C significantly reduced surface nickel species. Under both static and flow conditions platelet activation on the heat-treated alloy was comparable to that on pure titanium and was significantly lower than that on polished NiTi. This study demonstrates that the risk of thrombotic complications associated with NiTi in vivo can be reduced through heat modification of the alloy surface to reduce surface nickel.     

Effect of ceramic conversion treatments on the surface damage and nickel ion release of NiTi alloys under fretting corrosion conditions

Recent researches have demonstrated that surface modification can improve the fretting wear resistance of NiTi alloys in air or enhance their aqueous corrosion resistance without fretting. However, little is known about the behaviour of surface engineered NiTi under fretting corrosion conditions. This is important for such body implants as orthodontic arch wires and orthopedic bone fixation devices because they need to withstand the combined attack of corrosion from body fluid and mechanical fretting. In this study, a NiTi alloy was ceramic conversion (CC) treated at 400 and 650 °C. The effect of the surface treatment on the fretting corrosion behaviour of NiTi alloy was investigated using fretting corrosion tests in the Ringer’s solution. The experimental results have shown that the CC treatment can convert the surface of NiTi into a TiO₂ layer, which can effectively improve the fretting corrosion resistance of NiTi alloy and significantly reduce Ni ion release into the Ringer’s solution. Detailed SEM observations revealed that the untreated samples were severely damaged by adhesion and delamination; the high temperature (HT) (650 °C/1 h) treated samples were damaged mainly by spallation and adhesion; and the low temperature (LT) (400 °C/50 h) treated samples were characterised by mild abrasion. Mild oxidation and corrosion were also observed for all three types of samples tested under fretting corrosion conditions.     

Effect of micro-arc oxidation surface modification on the properties of the NiTi shape memory alloy

In this paper, the effects of micro-arc oxidation (MAO) surface modification (alumina coatings) on the phase transformation behavior, shape memory characteristics, in vitro haemocopatibility and cytocompatibility of the biomedical NiTi alloy were investigated respectively by differential scanning calorimetry, bending test, hemolysis ratio test, dynamic blood clotting test, platelet adhesion test and cytotoxicity testing by human osteoblasts (Hobs). The results showed that there were no obvious changes of the phase transformation temperatures and shape memory characteristics of the NiTi alloy after the MAO surface modification and the coating could withstand the thermal shock and volume change caused by martensite-austenite phase transformation. Compared to the uncoated NiTi alloys, the MAO surface modification could effectively improve the haemocopatibility of the coated NiTi alloys by the reduced hemolysis ratio, the prolonged dynamic clotting time and the decreased number of platelet adhesion; and the rough and porous alumina coatings could obviously promote the adherence, spread and proliferation of the Hobs with the significant increase of proliferation number of Hobs adhered on the surface of the coated NiTi alloys (P?<?0.05).