CN200710053095．3一种纳米复合类金刚石涂层制备方法

本发明公开了一种纳米复合类金刚石涂层制备方法,利用磁场控制的阴极电弧放电,通人乙炔气体使金属靶前乙炔过量,靶面形成金属碳化物层,当电弧运动时从靶面蒸发出金属碳化物,此外电弧靶前方在辅助磁场作用下利用电弧放电产生的强等离子体离化乙炔气体,产生高度离化的碳离子,在偏压的作用下,从靶面蒸发的金属碳化物和乙炔产生的碳离子在工件表面形成碳化物掺杂纳米复合类金刚石涂层。本发明制备类金刚石涂层具有涂层硬度高、     

类金刚石碳膜的研究进展

从类金刚石碳膜作为耐磨薄膜的角度出发，综述了近年来类金刚石碳膜(DLC)结构、沉积技术、沉积机理和性能方面的相关研究进展。介绍了DLC的相结构、过滤阴极真空弧(FCVA)、类金刚石碳膜的沉积机理及主要工艺影响因素，同时指出了存在的问题及研究发展趋势。     

材料表面处理新技术

1离子沉淀金刚石薄膜技术 在成品刀具表面沉积一层类金刚石薄膜或在其他基板上沉积一层金刚石薄膜取下后再焊在刀具表面。制备金刚石薄膜的原理是首先制备出离子态碳,然后使其在工件表面重新晶化而得,由于非晶态碳和石墨的存在,实际上多数情况下获得的是类金刚石薄膜。     

超低摩擦WS_2/W-DLC固体润滑薄膜的制备与性能

利用离子束辅助沉积技术和低温离子渗硫技术制备了二硫化钨/钨掺杂类金刚石(WS2/W-DLC)复合薄膜。采用扫描电子显微镜(SEM)、拉曼光谱仪(Raman)、透射电子显微镜(TEM)、纳米硬度仪(Nano-indenter)和多功能摩擦磨损试验机(UMT)考察了薄膜的微观结构与摩擦学性能。结果表明:制备的薄膜在大气环境下表现出优异的力学性能和超低摩擦的性能,该复合薄膜中,硬质强化相纳米碳化物WC1-x和软质润滑相过渡族金属硫化物WS2、Fe S均匀镶嵌于类金刚石基体内形成复合结构,复合结构是薄膜表现出优异性能的主要原因。     

元素掺杂对类金刚石薄膜摩擦学性能的影响

类金刚石碳薄膜具有良好的润滑性能,摩擦界面的磨屑或摩擦层结构影响其摩擦行为。掺杂的类金刚石碳薄膜是一个重要类别,其特征在于在非晶碳结构中结合不同的元素,改善其力学、摩擦学、电化学等性能。报告了不同非金属及金属元素的掺杂对类金刚石碳薄膜性能的影响,讨论了摩擦学性能随其化学组成和微观结构的变化,尽可能获得其间的一般趋势或相关性,并对元素掺杂类金刚石薄膜的发展进行了展望。     

纳米片状金刚石膜的生长过程

采用微波等离子化学气相沉积系统（MPCVD）在镀钛的单晶硅衬底上制备纳米金刚石薄膜。反应气体为CH4和H2,其流量比为1∶1,微波功率为1 800 W,反应气压为10 kPa。利用扫描电镜（SEM）和Raman光谱分析薄膜的形貌和碳结构。结果表明,纳米金刚石薄膜呈现片状的组织特征,其生长过程为：生长初期在单晶硅衬底上形成由纳米碳颗粒组成的球状碳团簇;随着沉积时间的增加,碳团簇逐渐增大,纳米碳颗粒定向排列或自组装,最终形成片状纳米金刚石膜。     

硅掺杂CVD金刚石薄膜

研究硅掺杂对CVD金刚石薄膜形貌、结构特性和成分的影响。通过向丙酮中加入正硅酸乙酯作为反应气体,在硅基底上沉积硅掺杂CVD金刚石薄膜。金刚石薄膜的表面形貌和显微组织由场发射电镜表征。金刚石薄膜的成分通过拉曼光谱和X射线衍射（XRD）进行研究。薄膜的表面粗糙度由表面轮廓仪评估。结果表明,硅掺杂会降低晶粒尺寸,促进晶粒细化并抑制三角锥形形貌。XRD研究表明,（111）朝向的晶面显著减少。拉曼光谱研究表明,硅掺杂会促进薄膜中硅碳键的形成以及非金刚石相的增多。在硅碳浓度比为1％时,沉积得到光滑的细晶粒金刚石薄膜。     

非平衡磁控溅射掺Ti类金刚石薄膜的结构分析

采用非平衡磁控溅射沉积技术在SCM415渗碳淬火钢基片上沉积了无氢Ti掺杂类金刚石(Ti-DLC)薄膜和无氢高纯类金刚石(DLC)薄膜,通过调节Ti靶的溅射功率使获得的Ti-DLC薄膜Ti含量(原子分数)为1.9%-34%.利用Raman分光光谱仪、XPS,XRD、显微硬度计及纳米划痕仪分析研究了Ti-DLC的组织结构、显微硬度及薄膜附着力.结果表明,利用非平衡磁控溅射得到的Ti-DLC薄膜,在Ti含量小于25%时,Ti-DLC薄膜仍具有类金刚石薄膜的sp2,sp3结构,但Ti的掺杂促进了sp3键向sp2键的转变.掺杂的Ti以TiC纳米晶的形式存在于非晶态的DLC中.掺杂Ti后薄膜的硬度明显降低,而薄膜附着力明显改善;但是当Ti含量超过3%后,薄膜附着力无明显变化,硬度逐渐回升.     

纳米复合薄膜水润滑摩擦学性能的研究进展

评述了类金刚石基(DLC、a-C)、非晶氮化碳基(a-CNx)、过渡金属氮化物基(TiN、CrN)及其改性纳米复合薄膜的水润滑摩擦学性能,分析了微观结构、梯度结构、元素掺杂、对磨材料及摩擦参数对其水润滑摩擦磨损性能的影响,并揭示了水润滑中纳米复合薄膜存在的摩擦磨损机制,指出了三种纳米复合薄膜体系在水润滑中均可表现出优异的减摩抗磨特性,但与薄膜成分、层状结构、力学性能及对磨材料物理化学性能密切相关。一般而言,相比于过渡金属氮化物基薄膜,类金刚石基及非晶氮化碳基薄膜由于在水润滑中形成转移层和水合润滑层而呈现出更低的摩擦系数和磨损率。当选用的对磨材料易于发生摩擦水合反应时,形成的水合层起到的保护作用使得纳米复合薄膜均表现出了更低的磨损率。在保证薄膜未发生剥落而失效时,适当地加载载荷和滑移速度也是获得最优水润滑摩擦学性能的关键因素。为薄膜应用在水润滑器械作业提供了一定的参考,并展望了纳米复合薄膜水润滑摩擦学未来的研究方向。     

高功率等离子磁控溅射法制备含钛类金刚石碳膜(英文)

为了改善类金刚石碳膜的性能,采用高功率等离子磁控溅射法将含钛非晶碳薄膜沉积在304不锈钢基材上,气源为C2H2-Ar混合气体,金属钛为阴极靶材。为了改善附着力和降低残余应力,制备了含Ti/TiC/DLC多层结构的镀膜。利用GDS、XRD、SEM、Raman光谱法、纳米压痕仪和盘-销摩擦计研究基材偏压及基材与靶材的距离对薄膜性能的影响。结果表明,薄膜具有优良的粘合强度和韧性。     

单晶金属衬底上多层石墨烯的可控生长进展

石墨烯作为一种理想的二维材料,具有机械性能好、电阻率低、热导率高等优点,受到人们的广泛关注。特别地,通过调控石墨烯层数可以改变石墨烯的电学性质,如带隙可调、半导体性质、特殊量子行为等,拓展石墨烯在柔性透明电极、高温超导、高性能传感等领域的应用。目前,人们已对金属衬底上高质量单层石墨烯的制备做了很多研究,发现当单层石墨烯覆盖金属衬底时,衬底将失去催化活性,使得高质量多层石墨烯的可控生长变得非常困难。为了制备多层石墨烯,研究人员已经探索了多种生长方法。总结了单晶金属衬底上多层石墨烯两种常见的生长模式,即表面成核控制的层层往上生长和偏析成核控制的层层往下生长,表面成核控制生长包括气源分子束外延、等离子体化学气相沉积等,偏析成核控制生长包括合金衬底偏析、单质金属衬底偏析等。针对多层石墨烯的各种生长方法,分别从成核密度、晶畴尺寸、层厚均匀性等方面进行了分析总结。最后,对该领域的发展趋势进行了展望,有助于为多层石墨烯的可控生长提供新的解决方案,促进多层石墨烯的发展与应用。     

Structural transition and magnetic properties of evaporated Fe/Gd multilayers

Fe/Gd multilayers were prepared by alternate vapor deposition of pure Fe and Gd at a rate of 0.01-0.03 nm/s in an ultra-high-vacuum electron-gun evaporation system.The effects of the constituent metal layer thickness on the microstructures and magnetic properties of the films were investigated by low angle X-ray diffraction,transmission electron microscopy,and vibrating sample magnetometer.The experimental results show that a transition from the polycrystalline to amorphous state in the Fe layers occurs with the decrease of Fe layer thickness in the Fe/Gd multilayers.The saturation magnetization of the muitilayers reduces significantly with decreasing Fe layer thickness and increasing Gd layer thickness.A superparamagnetic behavior at room temperature is observed for the [Fe(0.6 nm)/Gd(4.0 nm)]15 multilayer due to the formation of discontinuous Fe layers.     

Surface morphology of nanostructured anatase thin films prepared by pulsed liquid injection MOCVD

Nanostructured anatase thin films were prepared by chemical vapor deposition feeding a metal organic precursor in a pulsed liquid injection mode. The films were deposited at 500 °C on stainless steel substrates using a single molecular titanium isopropoxide liquid solution as the precursor, without any reactant gas. An effective pulsing injection mechanism for the precursor supply provides uniform concentration of the precursor in the vapor phase, allowing the formation of titanium dioxide layers from small micro-doses of the metal organic precursor. Energy-dispersive spectroscopy, scanning electron microscopy and X-ray diffraction studies show the formation of crack-free nanostructured anatase thin films, highly oriented, formed basically by stepwised nanostructures with a uniform coverage and no detectable carbon contamination. Surface crystallinity, composition, nanostructure and morphology are discussed in terms of the experimental parameters used in the deposition process.     

MoS2/Pb-Ti多层薄膜的结构和摩擦学性能

目的 设计MoS2/Pb-Ti多层薄膜,改善真空和大气环境下的摩擦学性能。方法 采用磁控溅射技术沉积MoS2/Pb-Ti多层薄膜,通过扫描电镜（SEM）、X射线衍射(XRD)、纳米压痕仪、真空和大气摩擦磨损实验,分别评价MoS2/Pb-Ti多层薄膜的表面形貌、微观结构、力学性能、真空和大气环境下的摩擦学性能,并通过光学显微镜、能谱仪（EDS）、Raman光谱仪对磨痕及磨斑进行分析。结果 随着MoS2层厚度的增加,MoS2/Pb-Ti多层薄膜的表面颗粒逐渐细化,变得更加光滑。同时,微观结构由金属相主导转变为由MoS2相主导,弹性模量逐渐降低,硬度则先升高后降低。在真空环境下,MoS2/Pb-Ti多层薄膜的摩擦系数低至0.01,磨损率低至2.2×10?7 mm3/(N?m),大气环境下摩擦系数低至0.07左右,磨损率低至2.7×10?7 mm3/(N?m)。 结论 在真空摩擦磨损实验中,MoS2层厚度过薄时,MoS2/Pb-Ti多层薄膜的磨损机制为粘着磨损,MoS2层厚度增加有助于形成稳定的转移膜,使得摩擦磨损大幅降低。在大气摩擦磨损实验中,Ti保护MoS2的结构免于H2O和O2的破坏,使体系具有低而稳定的摩擦磨损。     

Cu/Ni多层膜对Ti811合金微动磨损和微动疲劳抗力的影响

在Ti811钛合金表面利用离子辅助磁控溅射沉积技术制备20～1200nm不同调制周期的Cu/Ni金属多层膜,分析多层膜的结构,测试膜基结合强度、膜层显微硬度和韧性,对比研究不同调制周期的Cu/Ni多层膜对钛合金基材常温下微动磨损性能和微动疲劳(FF)抗力的影响。结果表明:利用离子辅助磁控溅射技术可以获得致密度高、晶粒细化、膜基结合强度高的Cu/Ni多层膜,该类多层膜具有良好的减摩润滑作用,因而改善了Ti811钛合金常温下抗微动磨损和微动疲劳性能;Cu/Ni多层膜对钛合金FF抗力的改善程度随膜层调制周期呈现非单调变化趋势,调制周期为200nm的Cu/Ni多层膜对钛合金FF抗力的提高程度最大,原因归于该膜层具有良好的强韧和润滑综合性能。     

Plasma and ion-beam-assisted deposition of multilayers for tribological and corrosion protection

Multilayers of Ti/TiN and Al/AlN were deposited on steel and silicon by magnetron sputtering and ion-beam-assisted deposition. Compositions and film thicknesses were determined by Rutherford backscattering. Hardness was measured with a dynamic ultramicrohardness tester. The corrosion protection potential in an aqueous environment was evaluated by electrochemical techniques. The results are discussed in terms of the structure and composition of the multilayer arrangement. It turns out that the multilayer coatings generally show a better corrosion protection performance than both the pure metal and the pure nitride films, with an optimum ratio of nitride film thickness to metal film thickness for a maximum corrosion protection effect. The hardness values are in between that of nitride single film and those of metal single films. Deposition of multilayers with the possibility of selecting the thickness ratio of metal to nitride film for particular mechanical and chemical requirements allows a controlled adaption of the film features to a given application problem.     

Structural and morphological modification of PDMS thick film surfaces by ion implantation with the formation of strain-induced buckling domains

Elastomer films with three-dimensional features self-organized into coherent and semi-coherent buckling domains were created by implanting different species of metal ions and combinations thereof, using a metal evaporation ion source, into quality polydimethylsiloxane films. As a result of the implantation process, functionalized discrete regions of strain-induced surface buckling were created, taking the forms of domains of parallel surface waves, semi-ordered regions and disordered regions. In addition, deep, strain-induced, V-shaped cracks were observed to penetrate well into the elastomer matrix. Characterization was via optical microscopy, X-ray diffraction, atomic force microscopy and high-resolution scanning electron microscopy (SEM) in the form of field emission SEM. It was found that controlling the localized strain by altering the metal ion species can control the frequency of the V-shaped cracks and the properties of the buckled areas. These observations and possible mechanisms for the formation of the cracks and domains are discussed in this paper.     

刻蚀工艺对四面体非晶碳膜生长及其性能的影响

目的研究不同等离子体刻蚀工艺对基体和四面体非晶碳膜(ta-C)的影响,并进一步考察不同电弧等离子体刻蚀时间对ta-C薄膜结构的影响。方法采用自主设计研制的45°单弯曲磁过滤阴极真空电弧镀膜设备,进行不同等离子体刻蚀以及ta-C薄膜的沉积。使用等离子体发射光谱仪表征离子种类及其密度,使用椭偏仪表征薄膜厚度,原子力显微镜表征刻蚀后的基体粗糙度,拉曼光谱仪和XPS表征薄膜结构,TEM分析薄膜的膜基界面结构。结果辉光刻蚀工艺中,作用的等离子体离子以低密度的Ar离子为主;而电弧刻蚀时,作用的等离子体离子为高密度的Ar离子和少量的C离子,并且能够在基体表面形成约15 nm的界面层,并实现非晶碳膜(a-C)的预沉积。随电弧等离子体刻蚀时间增加,ta-C薄膜的sp3含量有所降低。结论相比于辉光刻蚀,电弧刻蚀利于制备较厚的ta-C薄膜。这主要是因为电弧刻蚀时,基体表面形成良好的界面混合层,并预沉积了非晶碳膜,形成a-C/ta-C的梯度结构,有助于增强膜基结合力。     

Development of a novel cathodic plasma/electrolytic deposition technique: Part 2: Physico-chemical analysis of the plasma discharge

A novel plasma system has been developed recently for the deposition of carbon and titanium thin films on metal and metal alloy substrates. Unlike other deposition techniques, the process occurs in liquid precursors and a plasma discharge is created and confined around the cathode in a superheated vapour sheath surrounded by the liquid phase. This paper presents a detailed analysis of the physico-chemical mechanisms underlying this process. A correlation has then been carried out between the voltage/current characteristics and the consecutive physical phenomena occurring during the process (vapour phase formation, plasma discharge initiation and evolution). The structure and composition of the produced TiO₂ films have been compared with the composition and physical characteristics of the plasma discharge. This analysis allowed the construction of a first dissociation and deposition mechanism for this new plasma system.     

金属材料表面纳米化研究与进展

大多数金属材料的失效都是从其表面开始的,进而影响整个材料的整体性能。研究表明,在金属材料表面制备纳米晶,实现表面纳米化,可以提升材料的表面性能,延长其使用寿命。金属材料表面纳米化是指利用反复剧烈塑性变形让表层粗晶粒逐步得到细化,材料中形成晶粒沿厚度方向呈梯度变化的纳米结构层,分别为表面无织构纳米晶层、亚微米细晶层、粗晶变形层和基体层,这种独特的梯度纳米结构对金属材料表面性能的大幅度提升效果显著。根据国内外表面纳米化的研究成果,首先对表面涂层或沉积、表面自纳米化以及混合纳米化3种金属表面纳米化方法进行了简要概述,阐述了各自优缺点,总结了表面自纳米化技术的优势,在此基础上重点分析了位错和孪晶在金属材料表面自纳米化过程中所起的关键作用,提出了金属材料表面自纳米化机制与材料结构、层错能大小有着密不可分的联系,对金属材料表面自纳米化机制的研究现状进行了归纳;阐明了表面纳米化技术在金属材料性能提升上的巨大优势,主要包括对硬度、强度、腐蚀、耐磨、疲劳等性能的改善。最后总结了现有表面强化工艺需要克服的关键技术,对未来的研究工作进行了展望,并提出将表面纳米化技术与电镀、气相沉积、粘涂、喷涂、化学热处理等...