Shabalovskaya Svetlana A, Tian He, Anderegg James W, Schryvers Dominique U, Carroll William U, Van Humbeeck Jan
Metallurgy and Material Science Department, Katholieke University Leuven, 3001 Leuven, Belgium.
Biomaterials. 2009 Feb;30(4):468-77. doi: 10.1016/j.biomaterials.2008.10.014. Epub 2008 Nov 8.
The patterns of Ni release from Nitinol vary depending on the type of material (Ni-Ti alloys with low or no processing versus commercial wires or sheets). A thick TiO(2) layer generated on the wire surface during processing is often considered as a reliable barrier against Ni release. The present study of Nitinol wires with surface oxides resulting from production was conducted to identify the sources of Ni release and its distribution in the surface sublayers. The chemistry and topography of the surfaces of Nitinol wires drawn using different techniques were studied with XPS and SEM. The distribution of Ni into surface depth and the surface oxide thickness were evaluated using Auger spectroscopy, TEM with FIB and ELNES. Ni release was estimated using either ICPA or AAS. Potentiodynamic potential polarization of selected wires was performed in as-received state with no strain and in treated strained samples. Wire samples in the as-received state showed low breakdown potentials (200 mV); the improved corrosion resistance of these wires after treatment was not affected by strain. It is shown how processing techniques affect surface topography, chemistry and also Ni release. Nitinol wires with the thickest surface oxide TiO(2) (up to 720 nM) showed the highest Ni release, attributed to the presence of particles of essentially pure Ni whose number and size increased while approaching the interface between the surface and the bulk. The biological implications of high and lasting Ni release are also discussed.
镍钛诺中镍的释放模式因材料类型而异(低加工或未加工的镍钛合金与商业用金属丝或板材)。加工过程中在金属丝表面生成的厚二氧化钛层通常被视为防止镍释放的可靠屏障。本研究针对生产过程中产生表面氧化物的镍钛诺金属丝展开,旨在确定镍释放的来源及其在表面亚层中的分布情况。运用X射线光电子能谱(XPS)和扫描电子显微镜(SEM)研究了采用不同技术拉制的镍钛诺金属丝表面的化学性质和形貌。利用俄歇电子能谱、聚焦离子束(FIB)透射电子显微镜(TEM)和电子能量损失近边结构谱(ELNES)评估了镍在表面深度的分布以及表面氧化物的厚度。采用电感耦合等离子体发射光谱法(ICPA)或原子吸收光谱法(AAS)估算镍的释放量。对选定的金属丝在未施加应变的初始状态以及经过处理的应变样品中进行了动电位极化测试。初始状态的金属丝样品显示出较低的击穿电位(200毫伏);这些金属丝经过处理后耐腐蚀性得到改善,且不受应变影响。研究表明了加工技术如何影响表面形貌、化学性质以及镍的释放。表面氧化物二氧化钛最厚(高达720纳米)的镍钛诺金属丝显示出最高的镍释放量,这归因于存在基本为纯镍的颗粒,其数量和尺寸在接近表面与基体的界面时会增加。文中还讨论了高且持久的镍释放所带来的生物学影响。