离子注入在医用钛及其合金表面改性中的应用

钛及其合金因具有较好的耐蚀抗磨性、生物活性、生物相容性以及在生理环境中的无毒性,成为医用领域中最常用的一种金属材料。但是,钛及其合金自身无抗菌性,表面摩擦因数大,抗塑性剪切能力低,且长期服役中易被环境污染和易于磨损失效,这些特性在一定程度上限制了其应用领域的扩展。因而,学者常采用离子注入技术对医用钛及其合金进行表面改性,以提升其表面性能,延长其制件服役寿命和扩展材料应用范围。研究表明,单一元素离子注入对提升钛及其合金的医用性能不够理想,因而学者采用金属+非金属、金属+金属离子进行复合注入,旨在提升改性层减摩抗磨、耐蚀性能的同时,增强改性层的生物活性及服役过程中的抗菌性。另外,对现有研究展开分析与综述后,提出了对医用钛及其合金的离子注入改性,将朝着进一步深入理论、模拟研究,多复合离子(特别是金属+金属+非金属复合离子)注入研究,高性能离子注入设备研发及其离子注入参数拟定与优化等方面发展。     

材料的等离子体基离子注入表面改性

简要总结了哈工大近10年来在材料的等离子体基离子注入表面改性方面的工作,包括铝合金、钛合金、轴承钢的等离子体基离子注入,等离子体基离子注入混合,以及等离子体基离子注入的工业应用等。     

Effect of nitrogen ion implantation dose on torsional fretting wear behavior of titanium and its alloy

Various doses of nitrogen ions were implanted into the surface of pure titanium, Ti6Al7Nb and Ti6Al4V, by plasma immersion ion implantation. Torsional fretting wear tests involving flat specimens of no-treated and treated titanium, as well as its alloys, against a ZrO₂ ball contact were performed on a torsional fretting wear test rig using a simulated physiological medium of serum solution. The treated surfaces were characterized, and the effect of implantation dose on torsional fretting behavior was discussed in detail. The results showed that the torsional fretting running and damage behavior of titanium and its alloys were strongly dependent on the dose of the implanted nitrogen ions and the angular displacement amplitude. The torsional fretting running boundary moved to smaller angular displacement amplitude, and the central light damage zone decreased, as the ion dose increased. The wear mechanisms of titanium and its alloys were oxidative wear, abrasive wear and delamination, with abrasive wear as the most common mechanism of the ion implantation layers.     

Ionenbeschuß als Methode in der Korrosionsforschung und -verhütung

Ion bombardment – a method for Investigating and preventing During the last years the technique of ion implantation gained increasing importance. It allows to introduce very element at any temperature in any material and to produce stable as well as metastable alloys. Applications for this method in corrosion science are pointed out in the light of results from different laboratories. First the stability of titanium and zirconium against thermal oxidation after ion bombardment is discussed. Then the passivation behaviour of iron irradiated with chromium and tantalum ions is mentioned. The third section deals with aqueous corrosion of iron and hydrogen evolution in diluted acids. The implantation of lead, gold and platinum is shown to modify the reaction rates by several orders of magnitude. Finally the possibility of using ion bombardment for the investigation of hydrogen embrittlement of metals is demonstrated. The results prove this method for the formation of alloys to allow studies being not accessible with more conventional techniques.     

贵金属在船用钛及钛合金表面改性中的应用

舰船用钛及钛合金耐磨性较差,在海水中会被腐蚀,贵金属表面改性剂可以改善其耐磨性,提高耐腐蚀能力。基于钛及钛合金性能特点的分析,综述了贵金属金和银在改善耐磨性,钯、钌、银和金在增强耐腐蚀能力方面的应用,介绍了离子注入、磁控溅射、双层辉光等离子技术等贵金属表面改性工艺,对改性层复合化、纳米化的发展趋势进行了分析。     

钛合金空蚀损伤及防护的研究进展

钛合金具有密度小、比强度高、耐蚀性好等优势,被广泛应用于诸多工程领域。由于钛合金存在表面硬度低、耐磨性差等缺点,导致其在过流部件中容易发生空蚀损伤,会降低钛合金构件的使用寿命,因此针对钛合金空蚀损伤行为及其防护措施的研究显得极为重要。概述了空蚀现象的作用机理和理论模型,详细介绍了材料自身的力学性能、表面状态、介质类型和溶液温度等对钛合金空蚀行为的影响,着重讨论了针对钛合金空蚀损伤的多种应对措施,如热处理、激光纹理加工、激光气体氮化、化学热处理、离子注入、添加缓蚀剂等技术,总结了相应方法提高钛合金抗空蚀性能的具体原因。其中,热处理技术通过改变钛合金自身的显微组织来提高其抗空蚀性能;激光气体氮化工艺可在钛合金表面形成硬质TiN相,以抵御空泡溃灭时的冲击;化学热处理技术在钛合金表面生成了致密的陶瓷层+固溶扩散层,缓解了空泡的溃灭能,延长了空蚀的孕育期;离子注入技术依靠注入离子在钛合金材料表面产生固溶强化、位错增值强化等效果,降低其空蚀损伤。最后对钛合金空蚀及防护研究的发展方向提出了展望。     

Friction and wear properties of UHMWPE against ion implanted titanium alloy

In this study, a new two-step plasma immersion ion implantation technique was developed and applied for the modification of Ti6Al4V alloy; firstly ion implanting with nitrogen at high temperature and followed with oxygen in high dose. A graded titanium oxide-titanium nitride film was obtained on the surface of the Ti6Al4V alloy. The contact angle and the microhardness of the modified alloys were measured. The friction and wear properties of UHMWPE rubbing against the modified alloys under lubrication of distilled water were investigated using a pin-on-disc tribometer. The wettability and the microhardness of the alloy surfaces were found to be increased significantly after ion implantation. The friction coefficient decreased by nearly 5 times and the wear resistance of UHMWPE increased by about 40 times against the ion implanted Ti6Al4V alloy. Many deep furrows were found on the surface of the un-implanted alloy and were absent in the ion implanted surfaces of the alloy.     

离子注渗复合表面改性技术研究进展

综合国内外研究现状,目前针对离子注渗复合表面改性技术已开展了大量的研究工作,然而还缺少对其进行系统介绍的研究报道。首先,对离子渗技术（离子渗氮、离子渗碳和离子渗硫）、离子注入技术（氮离子注入、碳离子注入和金属离子注入）和离子注渗复合技术的原理进行了介绍。其次,对上述表面改性技术的研究进展进行了综述和总结。最后,针对目前离子注渗复合技术的不足之处,从改善硬件设备、强化作用机理、系统研究复合处理工艺和促进其工业化应用等方面进行解决,提出要充分利用注渗和镀膜技术复合的优势来实现材料结构功能一体化,推动多相复合强化技术的研究与开发,为工业化应用奠定理论基础。     

航空钛合金防氧化离子注入技术

针对飞机钛合金所存在的氧化损坏问题，通过使用几种金属离子注入钛合金后性能变化的分析研究，说明运用离子注入技术可以有效地防止钛合金的氧化。同时也分析了离子注入技术的优点及存在的不足，并展望了该技术在航空领域中的发展趋势。     

Thermal effect of ion implantation with ultra-short ion beams

Ion implantation with plasma guns operated in the detonation mode presents several differences from normally used low current ion implanter systems.

The most important differences are the high power of the beams generated with the plasma guns owing to their pulsed nature on one hand, and the plasma environment in which the target is immersed during the process of implantation on the other hand. Both effects were studied in this work.

The temperature profiles and their evolutions during and after nitrogen implantation in pure titanium, stainless steel and copper were investigated by using the finite differences method. The calculation for nitrogen ion implantation (fluence of 10¹³ cm⁻² and pulse time of 400 ns) in pure titanium, shows melting layers of 20 ns after the first 200 ns of implantation, with a fast cooling after the end of implantation. Thermal gradients of 1000 K μm⁻¹ and a heating rate of 5 K ns⁻¹ were also observed.

Optical spectroscopy observations (real time spectroscopy) of the implantation region show a highly activated nitrogen plasma.

Both effects can be of extreme importance in several applications such as, for example, titanium nitriding because of an extra temperature assisted absorption by the getter effect.     

中频交流磁控溅射制备氧化锌铝(ZAO)薄膜的研究

等离子体浸没离子注入与沉积技术可实现复杂形状零件表面垂直、均匀地离子注入与沉积处理,在材料表面改性领域具有广泛的应用前景。在技术发明后的20年间,该技术得到了快速的发展,但是也遇到了如何提高离子注入效率和注入均匀性、内表面注入、大面积注入等一系列问题。若上述问题得到解决,将极大的推进等离子体浸没离子注入与沉积技术的工业应用进程。     

SURFACE MODIFICATION OF TITANIUM FILMS WITH SODIUM ION IMPLANTATION： SURFACE PROPERTIES AND PROTEIN ADSORPTION

Sodium implanted titanium films with different ion doses were characterized to correlate their ion implantation parameters. Native titanium films and ion implanted titanium films were characterized with combined techniques of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and light microscopy (LM). The surface presented increased sodium concentration on treated titanium films with ion dose increasing, except for the group with the highest ion dose of 4× 1017 ions/cm2. XPS depth profiling displayed that sodium entered titanium film around 25-50 nm depth depending on its implantation ion dose. AFM characterization showed that sodium ion implantation treatment changed the surface morphology from a relatively smooth titanium film to rough surfaces corresponding to different implantation doses.After sodium implantation, implanted titanium films presented big particles with island structure morphology. The surface morphology and particle growth displayed the corresponding trend.Fibrinogen adsorption on these titanium films was performed to correlate with the surface properties of treated titanium films. The results show that protein adsorption on ion-implanted samples with dose of 2 × 1017 and 4 × 1017 are statistically higher (p ＜ 0. 01) than samples treated with dose of 5×1016 and 1 ×1017, as well as the control samples.     

The effect of surface modification on fretting fatigue in Ti Alloy turbine components

Severe fretting damage has been observed on the pressure surfaces of fan and compressor blade dovetails/disks in an aerospace gas turbine engine. A study has been carried out to evaluate the effect of an ion implantation technique in combination with the presently used surface treatments, such as shot peening and coating, on the fretting fatigue life of titanium alloy gas turbine engine components. The results from fretting fatigue tests, residual stress measurements, and nanoindentation tests were used to quantitatively evaluate the effect of various surface treatments on the fretting fatigue life of the fan blade and disk materials. Results from microstructural characterization and analyses of elemental and phase distributions within the implanted region are used to understand the effect of ion implantation on the surface properties of the alloys. Finally, an attempt has been made to evaluate the potential for improving the fretting fatigue life of the engine components using various surface modification techniques.     

变形镁合金表面改性的新技术

简述了对变形镁合金进行改性的必要性。对变形镁合金进行表面改性的方法包括激光熔敷、热喷涂、电化学方法、转化膜、液相/气相沉积、涂装和离子注入。对变形镁合金表面的热喷涂包括火焰喷涂和等离子喷涂;电化学方法包括微弧氧化和阳极氧化法;制备转化膜的方法包括化学镀、磷化和溶胶—凝胶法;离子注入包括高温金属离子注入和等离子体注入。指出应该加强对实际的变形镁合金构件的表面改性技术的开发,尤其是对试样研究较多的微弧氧化法、阳极氧化法和磷化。     

The effect of ion implantation on the corrosion behaviour of pure iron—II. Chromium ion implantation

As part of a programme to investigate the effect of ion implantation on the corrosion behaviour of iron, pure iron specimens have been implanted with doses of 5 × 10¹⁴ and 2 × 10¹⁵ chromium ions/mm². Using a three-sweep potentiokinetic polarization technique the corrosion behaviour of these surface alloy layers has been compared with that of conventional binary FeCr alloys containing from 0.8 to 12.5 wt%Cr. It was found that apart from a slight thickening of the air-formed oxide film induced by the ion implantation process, the polarization behaviour of conventional alloys and of alloys produced by ion implantation was qualitatively very similar. Quantitatively the low dose chromium implanted specimens corresponded to a conventional Fe-4.9%Cr alloy while the high dose chromium implanted specimens resembled conventional alloys containing x12.5%Cr. These data provide a sound basis for the interpretation of the potentiokinetic polarization and corrosion behaviour of the novel surface alloy layers which can be produced by ion implantation.     

High-current metal ion implantation for industrial applications

Ion implantation, as an efficient surface processing technique, has developed to include the implantation of various metallic ions for improving not only wear properties, but also such other surface properties as solid lubrication, fatigue, chemical stability, and engineering reliability. The high-dose metal ion implantation that can be accumulated in a short time over a relatively large implanting area makes metal vapor vacuum arc (MEVVA) source ion implantation well suited to practical surface engineering modification applications.     

氯对TiAl基合金高温氧化行为的影响

研究了表面喷沙少量ＭｎＣｌ２及离子注入氯对ＴｉＡｌ基合金９５０℃恒温氧化行的影 响ＴｉＡｌ合金９５０℃氧化后氧化膜为ＴｉＯ２及Ａｌ２Ｏ３的混合物,表面涂少量ＭｎＣｌ２后, 合金氧化速度降低了４个数量级,氧化膜的成分主要为Ａｌ２Ｏ３,离子注入Ｃｌ在氧化初期也显著降低 了氧化速率,延迟了ＴｉＯ２形成时间。     

医用多孔金属的制备及其生物活化研究进展

医用多孔金属材料,特别是多孔钛及钛合金能够提供与人体骨组织相匹配的力学性能,并促进骨组织长人以提高其与骨的固定度,在人体硬组织修复与替换方面具有广泛的应用前景。重点围绕多孔钛及钛合金的制备方法及适用于其复杂孔隙结构的表面生物活化方法,综述了各种方法在多孔钛及钛合金上的应用现状。目前适用于多孔钛及钛合金制备的技术主要有粉末冶金法、钛纤维烧结法、自蔓延高温合成法、选区电子束熔化技术和选区激光熔化技术,适用于多孔钛及钛合金表面生物活化的技术主要有溶胶凝胶法、仿生矿化法、电化学沉积法和微弧氧化法。多孔钛及钛合金的力学相容性和表面生物活性需要同时满足临床要求,才能进一步扩大其在医学领域的应用范围。     

镁合金和钛合金表面着色工艺研究进展

表面着色技术能在材料表面形成不同颜色的保护性膜层,在提高材料表面性能的同时,又可赋予产品漂亮的外观或实现消光等目的。表面着色有两种形式:一是,所生成的化合物自身具有一定的颜色;二是,光线的反射、折射、干涉等效应而使表面呈现不同颜色。作为两类重要的结构材料,镁合金和钛合金因其各自优良的性质被应用于诸多领域。综述了镁合金和钛合金表面着色工艺研究进展,介绍了镁合金和钛合金表面着色工艺研究及应用现状。镁合金表面着色工艺包括:化学转化+喷涂、金属涂层、有机涂层、阳极氧化和微弧氧化;钛合金表面着色工艺包括:热氧化、化学氧化、阳极氧化和微弧氧化。列举了应用于镁合金和钛合金表面着色的具体工艺参数,总结了两种合金表面着色的具体应用。镁合金和钛合金部件经表面着色处理后,可以兼顾轻量化和强度要求,并实现部件外观的装饰性。基于镁合金和钛合金表面着色工艺研究的现有成果,对镁合金和钛合金表面着色的研究提出了一定展望。     

Effect of the pressure in the gas-discharge chamber on the depth of nitrogen diffusion in titanium alloys

Among all the kinds of surface hardening of titanium alloys ion nitriding in a hydrogen-free medium is the most efficient and environmentally safe. The time of nitrogen saturation of titanium alloys by this method is 10–15 times shorter than in conventional nitriding. The acceleration of the diffusion of nitrogen under conditions of a glow discharge makes it possible to conduct the nitriding of (α+β)-titanium alloys at low temperatures that correspond to those of their aging, which had been impossible earlier. Diffusion saturation in ion surface impregnation is a multifactor process, which makes it controllable. One of the main controlling factors of ion nitriding is the pressure of the working gas. A study of the effect of the pressure in the gas-discharge chamber on the depth of nitrogen diffusion in titanium alloys (under conditions of stable existence of the glow discharge) made it possible to determine the dependence of the thickness of the layer and the specific power of the discharge on the nitrogen pressure and to determine the interrelation between the specific power and the saturating capacity of the gas medium. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 9, pp. 32–35, September, 1998.