Ti6Al4V合金表面离子注入N+C,Ti+N和Ti+C性能研究

采用等离子体基离子注入的方法在Ti6Al4V合金表面分别注入N+C、Ti+N和Ti+C元素,注入剂量均为2×1017 ions/cm2,N+C和Ti+N元素的注入负脉冲偏压为-50 kV,Ti+C元素的注入电压分别为-20 kV、-35 kV和-50 kV。通过X射线光电子能谱仪（XPS）和X射线衍射仪（XRD）对注入层进行了微观结构分析,结果表明：Ti+C注入层中存在TiC和Ti-O,Ti+N注入层中存在TiN和Ti-O键。采用纳米压痕仪和球盘磨损试验机对注入层的硬度和摩擦学性能进行了研究。结果表明：在相同注入电压下,Ti+C注入层的硬度最高,其次是Ti+N注入层,N+C注入层的硬度最低;Ti+C 注入层的硬度随着注入电压的增大而增大,最大硬度为11.2GPa。50kV注入层Ti+C具有最低的比磨损率,其值为6.7×10-5mm3/N.m,比磨损率较未处理Ti6Al4V基体下降了1 个数量级以上,表现出优异的耐磨损性能。     

铝合金等离子体基离子注入氮／钛层的结构

用X射线光电子能谱（XPS）和小掠射角X射线衍射（GXRD）研究了铝合LY12等离子体基离子注入氮／钛改性层的结构。结果表明。氮在注入层呈高斯分布,而钛沿注入方向逐渐减少。钛的注入对已注入的氮的分布有重要影响。钛的等离子体密度直接影响钛在改性层中的成分、相结构。改性层主要由TiO2,Al2O3,Aln,TiAl3,TiN或Ti组成。     

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采用MEVVA离子源技术对由磁过滤阴极真空电弧沉积的TiN薄膜注入不同剂量的Si元素,利用XPS和纳米硬度仪表征Si离子注入后化学成分、元素键合状态以及硬度的变化。结果表明,Si离子注入后,薄膜表面硬度得到提高,5×1016 ions/cm2的样品硬度峰值从27.18GPa增加到39.85GPa,随着注入剂量的增加,纳米硬度峰值有下降的趋势,1×1017 ions/cm2的样品硬度峰值为33.27GPa,但表面改性层的深度增加,纳米硬度在一定的深度范围内得到了整体的提高。离子注入使薄膜表面层的弹性模量显著提高,表层弹性模量随注入剂量的增加而提高。并且由于Si元素的注入,形成了新的微结构相Si3N4,新相的含量与注入剂量有关。     

SURFACE ANALYSES OF NITROGEN ION IMPLANTED Ti6Ai4V ALLOY

The techniques for surface analysis including AES,XPS and SIMS were employed to studythe chemical composition and bond valence of nitrogen ion implanted surface of surgicalimplantation service alloy Ti6Al4V.The depth of implanted nitrogen ions and the sputteringrate of argon beams were determined using a profilometer.It was found that the combinationof injected nitrogen ions with titanium resulted in the formation of hard TiN particles and theprofile of nitrogen concentration approximately displayed gaussian distribution.The totaldepth of implanted nitrogen is about 350 nm and its maximum concentration appears in thedepth of about 140 nm from the surface,in which the concentration ratio of nitrogen totitanium may be up to 1.1.     

MICROSTRUCTURE AND INDENTATION BEHAVIOUR OF MULTILAYER Ti-N FILM

The microstructure of Ti/TiN multilayer film was studied.It was shown by trans-mission electron microscopy of cross-sectional sample and respective secondary neutralsmass-spectroscopy depth profiling that the film has a periodic alternate multilayeredstructure:substrate /FeTi/Ti/Ti_2N/TiN/Ti_2N/Ti/Ti_2N/TiN...Ti/Ti_2N/TiN,whereFeTi and Ti_2N were the transition layers formed during ion plating.Cross-sectionalfracture surface of indentation samples had been obtained and studied with scanningelectron microscopy.It was shown that the multilayer film deformed during indentation,formed an indentation pit and a pile-up of materials around the indentation pit.As theapplied load increased deformation region extended beyond the film/substratc interfaceand into the substrate,the interlayer crack in the film and hole formation at the film/substrate interface were initiated.It is also shown that the multilayered Ti/TiN filmoffered better toughness in comparison with single layer TiN film.     

空气等离子体基注入Ti6Al4V合金摩擦学性能研究

采用空气等离子体基离子注入技术对Ti6Al4V合金进行了表面改性。注入负脉冲电压分别为10kV,30kV,50kV,注入剂量为0.6×1017ions/cm2。用X射线光电子能谱仪对注入层元素分布进行了分析,结果表明:改性层的外层为TiO2,外层与内层基体之间存在Ti2O3、TiO、TiN;采用球盘磨损试验机对注入层的摩擦学性能进行了研究。结果表明:随着注入电压的增加,摩擦因数减小,耐磨性能提高。且以50kV注空气最为显著,摩擦因数较基体降低了3倍多,磨损体积与比磨损率较基体均下降了1个数量级以上。注入层硬度比基材Ti6Al4V也有明显提高。     

EVOLUTION OF MICROSTRUCTURE OF LASER SURFACE ALLOYING OF γ TiAi ALLOY WITH NITROGEN

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氮离子注入的Ti6Al4V表面分析

利用表面分析技术(AES,XPS,SIMS)研究了经氮离子注入的外科植入材料Ti6Al4V表面成分与键合态,用轮廓仪的测量结果计算了氮离子注入深度及注入氮离子的Ti6Al4V的刻蚀速率。考虑到该合金的基体效应,对AES的定量结果进行了修正。结果表明,注入到合金中的氮离子与合金中的Ti形成高硬度的TiN,N的分布近似为Gauss形式,注入总深度约为350nm,在距表面约140nm处氮量最大,N与Ti的浓度比可达1.1。     

等离子渗氮与喷丸强化复合改进钛合金抗微动损伤性能

利用直流脉冲等离子电源装置对Ti6A14V钛合金表面渗氮处理,研究了渗氮层的相组成、硬度分布、韧度及摩擦学性能,采用喷丸形变强化(SP)对渗氮层进行后处理,以达到联合提高钛合金微动疲劳(FF)抗力的目的.研究结果表明:脉冲电源等离子技术可在钛合金表面获得由TiN、Ti2N、Ti2A1N等相组成的渗氮层,该改性层能够显著地提高钛合金常规磨损和微动磨损(FW)抗力,但降低了基材的FF抗力.渗氮层的减摩和抗磨性能与SP引入的表面残余压应力协同作用,使钛合金FF抗力超过了SP单独作用.提高渗氮层韧度对改善钛合金FF和FW性能均十分重要.     

离子注入对TC4钛合金TiN/Ti涂层结合力和抗砂尘冲蚀性能的影响

目的通过离子注入提高TiN/Ti涂层的结合力和抗冲蚀性能。方法先采用金属蒸气真空弧(MEVVA)离子源在TC4基体上分别注入四种离子(Mo、Ti、Nb、Co),再用磁过滤真空阴极弧(FCVA)技术制备TiN/Ti涂层。采用非球面测量仪、AFM、XRD和纳米压痕仪,对四种离子注入的TC4基体表面粗糙度、表面形貌、物相结构、纳米硬度和弹性模量进行表征,采用划痕仪测量涂层的结合力,采用涂层冲蚀考核平台对不同试样进行砂尘冲蚀性能试验。结果经过Mo、Ti、Nb离子注入的TiN/Ti涂层的结合力和抗冲蚀性能都有提高,其中Mo离子注入的TiN/Ti涂层的结合力达71 N、耐冲蚀时间为80 min,与未离子注入涂层相比,分别增加31.5%和77.8%,而平均冲蚀率降低39.5%,仅为0.0078mg/g。Co离子注入的TiN/Ti涂层的结合力仅为40 N,平均冲蚀率增大了19.0%,达0.0433 mg/g,其抗砂尘冲蚀性能明显下降。结论离子注入涂层的抗砂尘冲蚀性能与结合力密切相关,随着结合力的增大,TiN/Ti涂层的平均冲蚀率减小,其耐冲蚀时间增加,选择合适的离子注入可提高TiN/Ti涂层的抗冲蚀性能。     

Electrochemical behavior of the Ti6Al4V alloy implanted by nitrogen PIII

Plasma surface treatments have been used very often to enhance the surface properties of metallic materials. In this work, Ti6Al4V titanium alloy was treated by nitrogen plasma immersion ion implantation (NPIII) in order to obtain improvements in its surface properties, such as corrosion resistance evaluated here. The microstructure and corrosion behavior of the implanted and unimplanted samples were evaluated, using, XRD, GDOES and potentiodynamic polarization and impedance electrochemical spectroscopy tests in 0.6 M NaCl solution. It was verified that the NPIII created resistant layers to corrosive attacks. In corrosion tests by polarization, the implanted samples showed corrosion current density reduction of about 10 times compared to the Ti6Al4V alloy without treatment. Besides that, it was also observed a reduction of the passive current density of one order of the magnitude. In all the studied cases, the polarization curves were shifted to more positive values of potentials, indicating a lower tendency of these PIII treated surfaces to corrosion. The implantation process produced a thin TiN surface layer followed by Ti₂N and then a layer with nitrogen in solid solution, all detected by GDOES combined with X-ray diffraction. These layers promoted an excellent polarization resistance of the Ti6Al4V surfaces on impedance spectroscopy tests also. This better performance in these tests can be correlated with the formation of continuous nitride layer, which could retard chloride ions ingress into the substrate.     

TiN单层和TiN/Ti(C,N)多层涂层的结构和性能研究

借助XRD、SEM、纳米压痕和划痕仪研究了采用磁控溅射在硬质合金基体上沉积的TiN单层和TiN/Ti(C,N)多层涂层的组织结构和力学性能。研究表明:TiN与TiN/Ti(C,N)多层涂层的晶粒形貌均呈柱状晶结构,而TiN/Ti(C,N)多层涂层形成了TiN、Ti(C,N)交替的调制结构。由于界面强化作用,TiN/Ti(C,N)多层涂层表现出比TiN更高的硬度及与基体更好的结合力。     

W、Mo离子注入对离子镀TiN薄膜表面结构和性能的影响

目的进一步改善氮化钛薄膜的摩擦学性能。方法利用金属蒸汽真空弧源(MEVVA)在离子镀TiN薄膜表面进行等剂量W、Mo离子注入。采用扫描俄歇系统、光学三维形貌仪、X射线衍射仪和纳米压痕仪,分别分析了TiN薄膜的离子注入深度、表面形貌及粗糙度、相结构和不同压入深度的薄膜硬度。在球盘滑动摩擦磨损试验机上考察了TiN薄膜的摩擦学性能,并利用扫描电子显微镜和三维形貌仪对其磨损形貌进行分析。结果等剂量离子注入后,TiN表面注入层中W离子的含量明显大于Mo离子,两种离子注入对TiN薄膜的表面形貌和硬度的影响较小。XRD结果表明,W离子和Mo离子注入后均发现了Ti_2N硬质相。两种离子注入均可以不同程度地降低TiN薄膜的摩擦系数和磨损率。结论 W、Mo离子注入均可显著改善TiN薄膜的摩擦学性能,但Mo离子更有利于其摩擦系数的降低,而W离子注入更有利于TiN薄膜磨损率的降低。     

Comparison of ZrN and TiN formed by plasma based ion implantation & deposition

ZrN and TiN films have been deposited on Si substrates without additional heating using plasma based ion implantation & deposition (PBII&D) with pulse voltage from 0 to 5 kV. High quality columnar films have been obtained in both systems with a slight nitrogen deficiency. For ZrN, a marked reduction of the growth rate was observed when depositing with pulse bias, which was not observed for TiN, caused presumably by different partial sputter yields. A transition of the texture from (111) to (200) is again present in both systems, however with the transition occurring at a different pulse bias. Hardness values of 18-20 GPa and 22-24 GPa have been observed for TiN and ZrN, respectively.     

调制周期对TiN/Ti多层膜组织结构和结合力的影响

为了阐明调制周期对薄膜微观组织及薄膜与基体结合力的影响,采用反应磁控溅射在Ti6Al4V基板上交替沉积了Ti层及TiN层制备了TiN/Ti多层膜。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、显微硬度仪和划痕仪测量分析了薄膜的晶体结构、微观组织、硬度以及薄膜与基体之间的结合力。研究结果表明:TiN/Ti多层膜中均存在TiN,Ti和Ti2N 3种相。TiN/Ti多层膜均以柱状晶方式生长,在调制周期较大(5层)时,TiN和Ti层的界面清晰;随着调制周期的减小(层数增加),TiN和Ti层的界面逐渐消失。与单层TiN薄膜相比,多层TiN/Ti薄膜的硬度显著提高;但随着薄膜层数的增加,多层TiN/Ti薄膜硬度略微降低。当调制周期为80nm(30层)时,薄膜与基体的结合力明显提高,达到73N。     

Effects of titanium-implanted pre-treatments on the residual stress of TiN coatings on high-speed steel substrates

This investigation examined how titanium ion implantation pre-treatment affects the residual stress of TiN coatings on M2 high-speed steel. Ions were implanted by metal plasma ion implantation. The adhesion strength of the TiN coatings was enhanced by pre-treatment that implanted Ti into the M2 tool steel substrate. The implanted substrate functioned as a buffer layer between the deposited TiN and the tool steel substrate, resulting in variations of the residual stress. The residual stress determined by glancing-angle XRD demonstrates that the deposited TiN films on ion-implanted substrates exhibited reduced compressive stress, from − 3.95 to − 2.41 GPa, which corresponded to a decrease in the grain size of the TiN films. The texture of the TiN film was clearly transformed from the preferred orientation of (220) to (111), subsequently enhancing wear resistance against a tungsten ball.     

Corrosion properties of CVD grown Ti(C,N) coatings in 3.5 wt-% NaCl environment

The corrosion behaviour of Titanium carbonitride (Ti(C,N)) films grown by chemical vapour deposition was analysed in artificial sea water environment. From potentiodynamic polarisation curves, two passivation zones were detected, which originated from an initial oxidation of TiC and TiN to TiO₂ followed by growth of the TiO₂ layer upon increased polarisation. X-ray photoelectron spectroscopy analyses verified the mechanism by detecting a gradual decrease in Ti(C,N) peaks accompanied by a gradual increase of oxidised Ti (e.g. TiO₂). It was likewise found that carbon in TiC mainly decomposes into carbonate species while the nitrogen in TiN remains elemental and likely escapes as nitrogen gas. Accordingly, Ti(C,N) behaves like a superposition of TiC and TiN with their individual oxidation behaviour, resulting in a highly corrosion resistant material.     

Oxidation of TiN and Ti(C,N) thin films deposited on titanium substrate

Single-layered TiN and functionally graded Ti(C,N) coatings were magnetron sputtered to a thickness of about 1 μm, and their oxidation behavior was studied. The Ti(C,N) coating oxidized as fast as the TiN coating, forming TiO₂ as an oxide layer. The nitrogen in the TiN and Ti(C,N) coatings tended to escape from the coating via the TiO₂ layer into the air. The carbon in the Ti(C,N) coating also had strong tendency to escape. Even before the complete oxidation of the coatings, the retained coating layer and the Ti-substrate were strongly enriched with oxygen.     

Hybrid elevated-temperature,low/high-voltage plasma immersion ion implantation of AISI304 stainless steel

Elevated-temperature plasma immersion ion implantation (PIII) is an effective non-line-of-sight technique to harden austenitic stainless steel by producing expanded austenitic phases in the near surface region. We report here a hybrid elevated-temperature, low/high voltage approach, which improves the efficiency while retaining the non-line-of-sight advantages of PIII. A low-voltage (4 kV), elevated-temperature (355°C) PIII process is first used to produce the modified layer, but the nitrogen concentration in this layer is typically relatively low and the thickness may not be adequate. This is followed by high-voltage (25 kV) PIII at a lower temperature to increase the nitrogen concentration and to achieve the desirable surface enhancement effects. To assess the efficacy of the technique, the samples are characterized using X-ray diffraction (XRD), nanohardness measurements, and secondary ion mass spectrometry (SIMS) depth profiling. The experimental results show that the nitrogen concentration increases by nearly 75% and the nitrogen penetration depth nearly doubles that of the low-voltage sample. The surface microhardness also improves by 150% and our data suggest that it is due to the formation of expanded austenites.     

Surface Modification of PVD-TiN Films Using MEVVAIon Implantation

IN severe working and operating conditions tin filmsfabricated by conventional methods may also fail.Therefore,the investigations were towards furthersurface treatments,aiming at modifying the wearresistance of TiN films.Among the post surfacetreatment methods,MEVVA ion implantation hasshown to be particularly promising for surfacemodification|2l Some studies have shown that the wearand friction of implanted TiN films were improved afterMEVVA ion implantation,irrespective of the type ofi…