Nb+C离子注入磁过滤真空电弧镀TiAlN薄膜研究

利用MeVVA离子源技术对阴极磁过滤真空弧沉积的TiAlN薄膜进行了不同注入剂量的Nb及Nb+C离子注入。采用EDS、TEM、GIXRD、显微硬度等测试方法研究了离子注入剂量对于薄膜微观结构和性能的影响。结果表明,注入剂量为Nb 5×1017ions/cm2+C 5×1017ions/cm2时,Nb在TiAlN薄膜内的注入投影射程为130 nm;在薄膜表层形成厚度约50 nm的非晶与纳米晶的复合结构;在次表层,晶粒发生局部扭曲变形。随着离子注入剂量的增加,薄膜与基底的复合硬度由HV 1 900增加到HV 3 000,在高剂量离子注入条件下,薄膜的硬度提升更为显著。     

ͬ������������X�������䷨

  利用磁过滤阴极电弧镀在硬质合金上沉积厚度约2~3 μm的TiAlN薄膜,并用MEVVA源离子对TiAlN薄膜注入金属离子V+和Nb+。应用北京同步辐射装置（BSRF）的同步辐射光源,采用掠入射X射线衍射（GIXRD）的方法对TiAlN薄膜表面离子注入层的微观结构进行分析研究。结果表明：未经过离子注入的TiAlN薄膜主要组成相是没有择优取向的Ti3AlN伴有少量AlN,而较小剂量(1×1017 ions/cm2)的离子注入都可以使Ti3AlN产生（111）上的择优取向和细化晶粒,且AlN消失;当离子注入的剂量达到5×1017 ions/cm2时,注入V+的Ti3AlN择优取向变为（210）,并产生TiN相;注入Nb+ 的各个衍射峰完全消失,说明TiAlN薄膜表面离子注入层被非晶化,结合透射电镜的研究结果,观察到非晶层的厚度约为80~100 nm。     

铜离子注入Ti6Al7Nb合金的表面改性研究

使用MEVVA强流金属源离子注入机对Ti6Al7Nb合金表面注入能量为80keV、剂量分别为0.5×1017,1×1017,2×1017,4×1017ions/cm2的铜离子,计算得到铜离子饱和注入量为2.15×1017ions/cm2。研究了注入的铜离子对Ti6Al7Nb合金腐蚀性能、显微硬度和磨损行为的影响,采用覆膜法研究了铜离子注入后试样对金黄色葡萄球菌的抗菌性能,并分析了注入剂量与抗菌性能的关系。结果表明,Ti6Al7Nb合金的硬度和耐磨性随着注入剂量的增加而提高,点蚀电位随着注入剂量的提高而下降。抗菌试验显示当注入量达到饱和注入量时,试样的抗菌率达到99%以上。     

TiN��Ĥ��������ע���΢�۽ṹ�ķ����о�

 利用磁过滤阴极电弧镀分别在硬质合金和高速钢基体上沉积厚度约2～3μm的TiN薄膜,并用MEVVA源离子注入装置对TiN薄膜注入金属离子V+和Nb+。应用北京同步辐射装置（BSRF）的同步辐射光源,采用掠入射X射线衍射（GIXRD）的方法对TiN薄膜表面离子注入层的微观结构进行了分析研究。结果表明：未经过离子注入的TiN薄膜均存在特定方向的择优取向,而较小剂量(1×10ˇ17ions/cm2)的离子注入可以使晶粒细化、择优取向减弱或改变;当离子注入的剂量达到5×10ˇ17ions/cm2时,TiN薄膜表面离子注入层被非晶化。结合透射电镜的研究结果,观察到TiN薄膜表面非晶层的厚度约为50～100nm,并简要地讨论了离子注入过程对微观结构的影响机制。     

同步辐射掠入射X射线衍射法研究TiA1N薄膜离子注入层的微观结构

利用磁过滤阴极电弧镀在硬质合金上沉积厚度约2～3μm的TiA1N薄膜,并用MEVVA源离子对TiA1N薄膜注入金属离子V+和Nb+.应用北京同步辐射装置(BSRF)的同步辐射光源,采用掠入射X射线衍射(GIXRD)的方法对TiA1N薄膜表面离子注入层的微观结构进行分析研究.结果表明:未经过离子注入的TiA1N薄膜主要组成相是没有择优取向的Ti3AlN伴有少量A1N,而较小剂量(1×1017ions/cm2)的离子注入都可以使Ti3AlN产生(111)上的择优取向和细化晶粒,且A1N消失;当离子注入的剂量达到5×1017ions/cm2时,注入V+的Ti3AlN择优取向变为(210),并产生TiN相;注入Nb+的各个衍射峰完全消失,说明TiA1N薄膜表面离子注入层被非晶化,结合透射电镜的研究结果,观察到非晶层的厚度约为80～100 nm.     

Si����ע���TiN��Ĥ��΢�۽ṹ����ѧ���ܵ�Ӱ��

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。     

Ti离子注入H13钢表面改性研究

利用MEVVA源强流离子注入机将Ti离子注入到H13钢表面,注入剂量和离子能量分别为0.5×1017~5.0×1017ions/cm2和105keV。利用TR IM2003程序模拟计算饱和注入剂量;通过显微硬度仪、磨损试验机、电化学测试系统和扫描电镜测试了注入前后H13钢的表面硬度、磨损性能、摩擦系数和耐蚀性。利用SEM、AES、XPS和EDX等分析手段对注入前后的材料表面形貌、注入元素的化学价态及浓度分布等进行分析。借助XPS考察了注入表面层钛元素的化学状态。结果表明,Ti离子注入显著提高了H13钢的表面硬度、耐磨性和耐蚀性,减轻了磨粒磨损;减轻了表面层铁元素的氧化。通过所测主要性能可知,利用钛离子注入改善H13钢较为经济有效的注入参数分别为1.0×1017ions/cm2和105keV。     

Nb离子注入对Zr-4合金耐蚀性能的影响

为了研究Nb离子注入对Zr-4合金电化学腐蚀性能的影响,对Zr-4合金试样表面进行不同剂量的Nb离子注入并测定其在1NH2SO4水溶液中的极化曲线,然后使用扫描电子显微镜(SEM)对极化实验后的试样表面形貌进行了观察。结果表明,Nb离子注入能够改善Zr-4合金的耐腐蚀性能,而且改善的程度与注入离子的剂量有关。同时使用X射线光电子能谱分析(XPS)对试样的表层成分和价态进行了分析,发现在注量为5×1016ion/cm2和1×1017ion/cm2的条件下,Nb和Zr在试样表层以Nb2O5和ZrO2的形式存在;而在注量为2×1017ion/cm2的条件下,则以Nb2O5,NbO和ZrO2的形式存在。     

钇和铈离子注入纯锆的腐蚀行为研究

为了研究铈,钇离子注入对纯锆耐蚀性的影响,纯锆样品用MEVVA源以40 kV注入1×1016 ions/cm2至1×1017 ions/cm2剂量的钇和铈,注入最高温度约为150℃.用X光电子谱仪(XPS)分析注入表层元素的价态;在1 mol/L硫酸溶液中3次极化测量来研究注入样品的耐蚀性.对于钇离子注入,当注入剂量大于5×1016 ions/cm2时,注入样品的耐蚀性显著提高.用掠角X射线衍射(GAXRD)研究氧化膜中由于铈离子注入发生的相转移.三次极化测量表明注铈样品与空白样品相比,耐蚀性下降许多.最后分别对注入钇和铈样品的腐蚀行为机理进行了探讨.     

碳离子注入纯锆后在1 mol/L硫酸溶液中的腐蚀行为

为了研究碳离子注入对纯锆耐蚀性的影响,用MEVVA源对纯锆样品进行了1×1016ions/cm2至1×1017ions/cm2的碳离子注入,注入加速电压为40 kV.用X射线光电子能谱(XPS)和俄歇电子谱(AES)分析了注入样品表层元素的价态和深度分布.透射电镜(TEM)用来观察碳离子注入样品的微观结构;碳离子注入样品后相结构的变化用掠角X射线衍射(GAXRD)来检测.纯锆注入样品随后浸入1 mol/L的硫酸溶液中,测其极化曲线以评价其耐蚀性.发现碳离子注入极大地提高了纯锆基体的耐蚀行为,剂量越高,耐蚀性越好.最后,对碳离子注入导致纯锆基体腐蚀行为发生改变的机理进行了讨论.     

Ti离子注入对石英玻璃表面金属化的影响

为提高石英玻璃表面金属化膜层与基底的结合强度,利用金属蒸发真空弧(MEVVA)离子源引出的Ti离子对石英玻璃及镀Ti膜石英玻璃进行离子注入,剂量选择3×1016,5×1016ion/cm2,模拟分析了注入离子能量的分布,采用卢瑟福背散射分析了注入Ti离子在基体中的深度分布,利用划痕实验机对比了镀Ti膜石英玻璃经Ti离子注入前后的膜基结合强度。实验结果表明:石英玻璃经Ti离子(5×1016ion/cm2)注入后,钛在基体中呈高斯分布,最大浓度分布在15~35 nm范围内;镀Ti膜石英玻璃经Ti离子(5×1016ion/cm2)注入后,最大浓度分布在5~15 nm范围内,注入离子穿透薄膜进入基材内部。Ti离子注入剂量为5×1016ion/cm2时,膜基的结合强度比未注入样品提高了90%。     

石墨烯纳米片对D16T铝合金微弧氧化膜层结构与性能的影响

目的研究石墨烯纳米片对D16T铝合金耐磨耐蚀性的影响,为铝合金表面微弧氧化处理技术在油气领域的应用提供理论依据。方法利用微弧氧化技术在含与不含石墨烯的电解液中在D16T铝合金表面制备微弧氧化膜层,采用XRD、SEM、EDS分析了膜层相结构和表面形貌,测试了膜层的粗糙度和显微硬度,通过摩擦磨损和电化学实验研究了石墨烯纳米片对D16T铝合金微弧氧化膜耐磨性和耐蚀性的影响。结果微弧氧化膜层主要由α-Al2O3和γ-Al2O3相组成,石墨烯的添加使Al2O3相的衍射峰值和衍射峰的数量增加,Al衍射峰明显降低;膜层表面平整,表面熔融颗粒较少,表面有大块团聚物堆积。膜层由外部疏松层和内部致密层组成,疏松层微孔数量和微裂纹较少,膜层厚度稍有增加,致密层厚度由不含石墨烯时的0.6μm增至1.6μm。含石墨烯的膜层容抗弧半径明显增加,Bode图中低频阻抗值由5×10^5Ω·cm^2提升至106Ω·cm^2,疏松层电阻由1.57×10^5Ω·cm^2增至1.98×10^5Ω·cm^2,致密层电阻由3.07×10^5Ω·cm^2提升至1.24×106Ω·cm^2;膜层自腐蚀电位由-0.53 V提高至-0.41 V,自腐蚀电流密度由3.15×10^-7 A/cm^2降低至3.97×10^-8 A/cm^2;膜层质量磨损量明显降低,摩擦系数减小,耐磨性增加。结论石墨烯纳米片通过放电通道进入膜层填充膜层中的孔和裂纹,部分石墨烯形成团状覆于膜层表面,使膜层更加平整、致密,膜厚增加,膜层耐磨性和耐蚀性得到明显提升。     

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.     

Effect of nitrogen ion implantation on the localized corrosion behavior of titanium modified type 316L stainless steel in simulated body fluid

Nitrogen ion implantation on titanium-modified type 316L stainless steel (SS) at the energy of 70 keV was carried out at different doses ranging from 1×10¹⁵ to 2.5×10¹⁷ ions/cm². These samples were subjected to open circuit potential (OCP)—time measurement, cyclic polarization, and accelerated leaching studies—in order to discover the optimum dose that can provide good localized corrosion resistance in a simulated body fluid condition. The results showed that the localized corrosion resistance improved with an increase in doses up to 1×10¹⁷ ions/cm², beyond which it started to deteriorate. The results of the accelerated leaching studies showed that the leaching of the major alloying elements was arrested upon nitrogen ion implantation. Gracing incidence x-ray diffraction studies showed the formation of chromium nitrides at a dose of 2.5×10¹⁷ ions/cm². X-ray photoelectron spectroscopy studies revealed the presence of these chromium nitrides in the passive film, which was attributed to the decreased corrosion resistance at a higher dose. Secondary ion mass spectroscopy studies on the passive film showed the variation in the depth profile upon nitrogen ion implantation. Thus, nitrogen ion implantation can be effectively used as a method to improve the corrosion resistance of the orthopedic implant devices made of titanium-modified type 316L SS. The nature of the passive film and its influence on corrosion resistance are discussed in this article.     

添加Y对电弧离子镀TiAlN薄膜结构和摩擦磨损性能的影响

目的 为进一步提高电弧离子镀TiAlN薄膜的摩擦磨损性能,研究添加元素Y对CrNi3MoVA钢表面电弧离子镀TiAlN薄膜微观组织结构、硬度、弹性模量及摩擦磨损性能的影响。方法 采用Ti-50Al和Ti-49Al-2Y合金靶,利用电弧离子镀技术在CrNi3MoVA钢表面制备两种氮化物薄膜,利用纳米压痕仪和摩擦磨损试验机分别测试了两种薄膜的硬度、弹性模量和摩擦系数,并用SEM、TEM、EDS、GIXRD分析了两种薄膜磨损前后的形貌、成分、相结构。结果 添加Y降低了TiAlN薄膜的晶粒尺寸,使其由柱状晶结构转变为近似等轴晶结构。TiAlYN薄膜的硬度较TiAlN薄膜提高了约25%,其弹性模量与TiAlN薄膜相近。与Si3N4对磨时,在加载载荷为20 N、往复行程为10 mm、往复速率为400 r/min的条件下,TiAlN薄膜的稳定摩擦系数为0.70~0.75,而TiAlYN薄膜的稳定摩擦系数为0.60~0.65,TiAlYN薄膜的磨损率较TiAlN薄膜的磨损率减小了约47%。TiAlN薄膜与TiAlYN薄膜的主要磨损机制均为刮擦磨损,TiAlN薄膜的失效机制主要是脆性裂纹导致的剥落。结论 添加Y对TiAlN薄膜具有明显的减摩耐磨作用,并提高了TiAlN薄膜在摩擦磨损过程中的抗开裂和抗剥落性能。     

Properties of Zr-ZrC-ZrC/DLC gradient films on TiNi alloy by the PIIID technique combined with PECVD

The Zr-ZrC-ZrC/DLC gradient composite films were prepared on TiNi alloy by the techniques combined plasma immersion ion implantation and deposition (PIIID) and plasma enhanced chemical vapor deposition (PECVD). With this method, the Zr-ZrC intermixed layers can be obtained by the ion implantation and deposition before the deposition of the ZrC/DLC composite film. In our study, an optimal gradient composite film has been deposited on the NiTi alloys by optimizing the process parameters for implantation and deposition. The surface topography was observed through AFM and the influence of the deposition voltage on the surface topography of the film was investigated. XPS results indicate that on the outmost layer, the Zr ions are mixed with the DLC film and form ZrC phase, the binding energy of C 1s and the composition concentration of ZrC depend heavily on the bias voltage. With the increase of bias voltage, the content of ZrC and the ratio of sp³/sp² firstly increases, reaching a maximum value at 200 V, and then decreases. The nano-indentation and friction experiments indicate that the gradient composite film at 200 V has a higher hardness and lower friction coefficient compared with that of the bare NiTi alloy. The microscratch curve tests indicate that gradient composite films have an excellent bonding property comparing to undoped DLC film. Based on the electrochemical measurement and ion releasing tests, we have found that the gradient composite films exhibit better corrosion resistance property and higher depression ability for the Ni ion releasing from the NiTi substrate in the Hank's solution at 37°C.     

Surface characteristics, nano-indentation and corrosion behavior of Nb implanted NiTi alloy

NiTi shape memory alloy has been modified by Nb implantation with different implantation parameters including incident dose and current. The surface morphology and chemical components are determined by atomic force microscopy (AFM), Auger Electron Spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results show that Nb implantation leads to the formation of compact Nb₂O₅/TiO₂ thin film about 30 nm in thickness on the surface of the NiTi alloy and decreases the surface concentration of Ni. A larger incident dose or incident current causes a higher surface roughness and a higher Nb content in the implantation layer of NiTi alloy. The nano-indentation measurements indicate the obvious reduction of both nano-hardness and Young's modulus of the Nb implanted NiTi alloy in the implantation layer and even in deeper NiTi matrix. The results of potentiodynamic polarization test show that the corrosion resistance of NiTi alloy in Hanks's solution has been evidently improved by Nb implantation. The NiTi alloy with a moderate implantation parameter of 1.5 × 10¹⁷ ions/cm² and 2 mA exhibits the best corrosion resistance ability.     

Surface characterization of passive film formed on nitrogen ion implanted Ti-6Al-4V and Ti-6Al-7Nb alloys using SIMS

The aim of this paper is to study the effect of N⁺ ion implantation on corrosion and phase formation on the implanted surfaces of Ti-6Al-4V and Ti-6Al-7Nb alloys. Nitrogen ion was implanted on Ti-6Al-4V and Ti-6Al-7Nb alloys at an energy of 70 and 100 keV, respectively using a 150 keV accelerator at different doses ranging from 5 × 10¹⁵ to 2.5 × 10¹⁷ ions/cm². Electrochemical studies have been carried out in Ringer’s solution in order to determine the optimum dose that can give good corrosion resistance in a simulated body fluid condition. The implanted surfaces of such modified doses were electrochemically passivated at 1.0 V for an hour. Secondary ion mass spectroscopy was used to study and characterize titanium oxide and titanium nitride layers produced on implanted surface and to correlate them with the corrosion resistance. The nature of the passive film of the implanted-passivated specimen was compared with the unimplanted-passivated as well as as-implanted specimens.